Surfactant compositions and use thereof

ABSTRACT

Surfactants capable of releasing and/or dissolving polymers to form water-soluble or water-dispersible polymer solutions are disclosed. In addition, polymer compositions containing a water-in-oil emulsion comprising the surfactant are provided and can be used, for example, in methods of dissolving a polymer. Also disclosed are detergent compositions and methods of cleaning articles and/or membranes using the surfactants herein. These surfactants and polymer compositions can be used in various industries including for water clarification, papermaking, sewage and industrial water treatment, drilling mud stabilizers, and enhanced oil recovery.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 62/773,676 filed on Nov. 30, 2018, the disclosure of which isincorporated herein by reference in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

THE NAMES OF PARTIES TO A JOINT RESEARCH AGREEMENT

Not applicable.

REFERENCE TO A SEQUENCE LISTING, TABLE, OR COMPUTER PROGRAM LISTINGAPPENDIX SUBMITTED ON A COMPACT DISC AND AN INCORPORATION-BY-REFERENCEOF THE MATERIAL ON A COMPACT DISC

Not applicable.

FIELD OF THE INVENTION

Inversion surfactants comprising the compounds described herein capableof releasing and/or dissolving polymers to form water-soluble orwater-dispersible polymer solutions are disclosed. In addition, polymercompositions containing a water-in-oil emulsion comprising the inversionsurfactant are provided and can be used, for example, in methods ofdissolving a polymer. These inversion surfactants and polymercompositions can be used in various industries including for waterclarification, papermaking, sewage and industrial water treatment,drilling mud stabilizers, and enhanced oil recovery. Also provided aredetergent compositions comprising the compounds described herein thatcan be used, for example, in methods of cleaning articles and/ormembranes.

BACKGROUND OF THE INVENTION

Various synthetic and naturally-occurring water-soluble orwater-dispersible polymers can be used in a variety of commercialapplications. These polymers are commercially available as powders,finely-divided solids, or water-in-oil emulsion polymers that requirethe polymer to be dissolved in water. While the polymers arewater-soluble or water-dispersible, it can be difficult to preparesolutions or homogeneous dispersions because of slow dissolution or slowdispersion into the water. Further, polymers can clump or remain asagglomerates on contact with water. Although these clumps eventuallydissolve or disperse using agitation, it can be impractical to agitatethe solution for a sufficiently long time to obtain complete dissolutionof the polymer particles.

Additionally, surfactants, and compositions thereof, can invert and/oractivate water-in-oil emulsion polymers to aid the dissolution anddispersion of those polymers. Such inversion surfactants can be used toincrease the dissolution of various emulsion polymers so the time fordissolution and degree of dissolution of the polymer is increased.

To reduce the time needed for polymer solids or inverse emulsionpolymers to dissolve or disperse in aqueous solution, an inversionsurfactant can be used.

Ethoxylated alkylphenols and alkylphenol-formaldehyde resins,particularly containing nonylphenol moiety as one of the building blockshave been used in the industry as one class of inversion surfactants.They also are used as surfactants for cleaning solutions and detergents.However, nonylphenols and their ethoxylated derivatives are known to betoxic, specifically as endocrine-hormone disrupters. Thus, there is aneed to replace these chemistries with nonylphenol-free alternativesthat are more environmentally friendly.

Because of the toxicity of nonylphenols and their ethoxylatedderivatives, industrial use has largely shifted to linear/branchedalcohol ethoxylates (LAEs). However, LAEs are generally not as effectiveas nonylphenol ethoxylates. Therefore, a need exists for novel inversionsurfactants that are effective for dissolving or dispersingwater-soluble or water-dispersible polymers in several industries or foruse as surfactants in cleaning applications.

BRIEF SUMMARY OF THE INVENTION

Disclosed herein are compounds and compositions useful as inversionsurfactants and/or detergent/cleaning compositions to aid in thedissolution of polymers or in the cleaning of membranes or articles. Forexample, disclosed herein is the compound of Formula 1 having thestructure of Formula 1:

wherein A is an optionally substituted phenyl, naphthalene, indole,purine, pyridine, quinoline, isoquinoline, pyrimidine, pyrole, furan,thiophene, imidazole, or thiazole; and Z has a structure of moiety A ormoiety B:

wherein X is —O—, —N(R₁₀)—, —OC(O)—, —C(O)O—, —N(R₁₀)C(O)—,—C(O)N(R₁₀)—, —OC(O)O—, —OC(O)N(R₁₀)—, —N(R₁₀)C(O)O—, or —N(R₁₀)C(O)N(R₁₀)—; n is an integer from 0 to 10; R₆ and R₉ are independentlyhydrogen, alkyl, or aryl; R₇ is alkyl, aryl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₀ is hydrogen, alkyl, or Z;R₁₁ is hydrogen or alkyl; m is independently an integer from 3 to 20;and z is an integer from 1 to 10.

The compounds of Formula 1 can have moiety B have the structure ofmoiety B1 or moiety B2:

wherein R₉ is independently hydrogen, alkyl, or aryl; and R₁₂ isindependently C₃ to C₂₂ alkyl or alkenyl.

The compounds of Formula 1 can have A be an optionally substitutedphenyl, naphthyl, pyridyl, quinolyl, or isoquinolyl.

The compounds of Formula 1 can have A be an optionally substitutedphenyl or naphthyl.

Further, the compounds can have the structure of Formula 2:

wherein R₁, R₂, R₃, R₄, and R₅ are independently hydrogen, Z, alkyl,alkoxyl, or two adjacent R groups combine to form a fused ring; Z has astructure of moiety A or moiety B:

wherein X is —O—, —N(R₁₀)—, —OC(O)—, —C(O)O—, —N(R₁₀)C(O)—,—C(O)N(R₁₀)—, —OC(O)O—, —OC(O)N(R₁₀)—, —N(R₁₀)C(O)O—, or —N(R₁₀)C(O)N(R₁₀)—; n is an integer from 0 to 10; R₆ and R₉ are independentlyhydrogen, alkyl, or aryl; R₇ is alkyl, aryl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₀ is hydrogen, alkyl, or Z;R₁₁ is hydrogen or alkyl; m is an integer from 3 to 20; and z is aninteger from 1 to 10.

The compounds of Formula 2 can have moiety B have the structure ofmoiety B1 or moiety B2:

wherein R₉ is independently hydrogen, alkyl, or aryl; and R₁₂ isindependently C₃ to C₂₂ alkyl or alkenyl.

The compounds of Formula 2 can have at least one of R₁, R₂, R₃, R₄, andR₅ be Z.

The compound of Formula 2 can have Z have the structure of moiety A, Xbe —O—; n be 0; R₁, R₂, R₃, R₄, R₅ be hydrogen; R₇ be —(CH₂)z-O—R₁₁, zbe 1, R₈ be hydrogen, R₁₁ be 2-ethylhexyl, and m be an integer from 7 to13 or an integer from 7 to 12.

The compounds can have the structure of Formula 3:

wherein R₁, R₂, R₄, and R₅ are independently hydrogen, alkyl, alkoxyl,or Z; and Z₁, Z₂, and Z independently have a structure of moiety A ormoiety B:

wherein X is —O— or —N(R₁₀)—; n is an integer from 0 to 5; R₆ and R₉ areindependently hydrogen or alkyl; R₇ is alkyl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₀ is hydrogen, alkyl, or Z;R₁₁ is hydrogen or alkyl; m is an integer from 3 to 20; and z is aninteger from 1 to 10.

The compounds of Formula 1 or 2 can have R₁, R₂, R₃, R₄, and R₅independently be hydrogen or C₁ to C₄ alkyl.

The compounds of Formula 1 or 2 can have R₁, R₂, R₃, R₄, and R₅ behydrogen.

The compounds of Formula 1, 2, or 3 can have R₆ and R₉ be hydrogen.

The compounds of Formula 1, 2, or 3 can have R₈ be hydrogen or methyl.

The compounds Formula 1, 2, or 3 can have R₇ be —(CH₂)z-O—R₁₁.

The compounds of Formula 1, 2, or 3 can have z be 1 to 3.

The compounds of Formula 1, 2, or 3 can have R₁₁ be C₄ to C₂₂ alkyl.

The compounds of Formula 1, 2, or 3 can have X be —O— or —N(R₁₀)—.

The compounds of Formula 1, 2, or 3 can have X be —O—.

The compounds of Formula 1, 2, or 3 can have X be —N(R₁₀)—.

The compounds of Formula 1, 2, or 3 can have R₁₀ be hydrogen.

The compounds can have a structure of Formula 4:

wherein R₁, R₂, R₄, and R₅ are independently hydrogen, alkyl, oralkoxyl; Z₁ is has a structure of moiety C

Z₂ has a structure of moiety D

n is an integer from 0 to 5; R₇ is alkyl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₁ is hydrogen or alkyl; m isan integer from 3 to 30; and z is an integer from 0 to 6.

The compounds having a structure of Formula 4 can have n be 0.

The compounds having a structure of Formula 4 can have R₇ be—(CH₂)z-O—R₁₁, and z be 1.

The compounds having a structure of Formula 4 can have R₈ be hydrogen.

The compounds having a structure of Formula 4 can have R₁₁ be2-ethylhexyl.

The compounds having a structure of Formula 4 can have m be an integerfrom 10 to 30.

Polymer compositions described herein can comprise a water-in-oilemulsion comprising an aqueous phase comprising water and awater-soluble or water-dispersible polymer, and an oil phase comprisingan oil and an emulsifying agent; and an inversion surfactant comprisingthe compound of Formula 1, 2, or 3 described herein.

The polymer compositions described herein can have the water-in-oilemulsion further comprise the inversion surfactant.

The polymer compositions can further comprise an aqueous solutioncontaining the inversion surfactant.

A polymer composition can also comprise a water-soluble orwater-dispersible polymer, an oil, a suspending agent, and the inversionsurfactant comprising a compound of Formula 1, 2, or 3 described herein.

Disclosed herein are also methods of dissolving the water-soluble orwater-dispersible polymer of the polymer compositions disclosed herein.The method comprising contacting the water-in-oil emulsion with theinversion surfactant.

The methods disclosed herein can have the water-in-oil emulsion furthercomprise the inversion surfactant and the water-in-oil emulsion iscontacted with an aqueous solution.

The methods can have the water-in-oil emulsion be contacted with anaqueous solution comprising the inversion surfactant.

The polymer compositions or methods can have the inversion surfactanthave a concentration of from about 0.1 wt. % to about 10 wt. % based onthe total weight of the emulsion.

The polymer compositions or methods disclosed herein can have theinversion surfactant have a concentration of from about 0.5 wt. % toabout 5 wt. % based on the total weight of the emulsion.

The polymer compositions or methods can have the polymer compositionsfurther comprise an ethoxylated C₁₀-C₁₆ alcohol; a C₁₂-C₁₃ primaryalcohol of linear and mono-methyl branched alcohol having on average 9moles ethylene oxide; an ethoxylate of a saturated C₁₂-15 alcohol; anethoxylated C₁₂-14 alcohol; an ethoxylated primary branched saturatedC₁₃ alcohol; an ethoxylated C₁₀ Guerbet alcohol; an ethoxylatedsaturated iso-C₁₃ alcohol; a saturated, predominantly unbranched C₁₃-15oxo alcohol having 11 ethylene oxide groups; a secondary alcoholethoxylate; a nonionic, alkoxylated alcohol; a polyoxyethylene (9)synthetic primary C₁₃/C₁₅ alcohol; an isotridecyl alcohol ethoxylatedwith an average of 9 moles ethylene oxide; an ethoxylated linear primaryC₁₂₋₁₄ alcohol; an ethoxylated nonylphenol;tert-octylphenoxypoly(ethoxyethanol); a tridecyl ether phosphate; apolyoxyethylene (5) soyaallylamine; a polyethylene glycol (PEG) 400monooleate; a PEG 600 monooleate; aPEG-25 castor oil; a PEG-30 castoroil; a PEG-40 castor oil; an aliphatic phosphate ester with 10 moles EO;an aliphatic phosphate ester with 6 moles EO; an oleic acid monoethanolamide with 14 moles ethylene oxide; a soyamine ethoxylate; or acombination thereof.

The methods described herein can have the inversion surfactant beactivated by contacting the inversion surfactant with an aqueoussolution.

The methods disclosed herein can have the inversion surfactant beactivated by contacting the inversion surfactant with an inversion aid.

The methods can also have the inversion aid comprise glycol, apolypropylene glycol, polyglycerol, urea, sorbitol, sucrose, glycerol, apolyglycerol, a phosphate, choline chlorine, guanidine,dioctyl-sulfosuccinate, malic acid, lactic acid,N-(phosphonomethyl)glycine, 2-phosphonopropanoic acid,3-phosphonopropanoic acid, 4-phosphonobutanoic acid, a phosphinosuccinicoligomer, a polyethylene glycol, urea, sorbitol, sucrose, glycerol, aphosphate, choline chlorine, or a combination thereof.

The methods can further have the aqueous solution contain a salt.

The methods can also have the temperature of the aqueous solution beincreased from about 2° C. to about 65° C.

Also provided are methods of preparing a compound of Formula 1, 2, or 3as described herein. The method comprises reacting compound (A) withcompound (B) to form compound (C); and further reacting compound (C)with compound (D) to form compound (F)

wherein A, X, R₆, R₇, R₈, R₉, n and m are as defined herein.

Still other methods of preparing the compounds described herein comprisereacting compound (F) with R—XH and an acid catalyst to form compound(G); and further reacting compound (G) with compound (D) to formcompound (H); or

reacting compound (F) with R—XH and a base catalyst to form compound(J); and further reacting compound (J) with compound (D) to formcompound (K);

wherein A, X, R₆, R₇, R₈, R₉, n and m are as defined in connection withthe compounds herein; and R is independently hydrogen or alkyl.

Detergent compositions are also provided. The detergent compositionsdisclosed herein can comprise a building agent and a surfactantcomprising the compound of Formula 1, 2, or 3 described herein.

Cleaning compositions are also provided. The cleaning compositionsdisclosed herein can comprise the compound of Formula 1, 2, or 3described herein. Optionally, the cleaning composition can furthercomprise a building agent.

Disclosed herein are also methods of cleaning an article. The methodcomprises contacting the article with a detergent composition comprisingthe compound of Formula 1, 2, or 3 as described herein.

In the methods of cleaning an article, the cleaning composition canfurther comprise a building agent.

The building agent can comprise an enzyme, an oxidizing agent, acondensed phosphate, an alkali metal carbonate, an alkali metalsilicate, an alkali metal metasilicate, a phosphonate, an aminocarboxylic acid, a carboxylic acid polymer, or a combination thereof.

The article can be a metal surface, a glass surface, a fabric, a ware, apolycarbonate surface, a polysulfone surface, a melamine surface, aceramic surface, a porcelain surface, or a combination thereof.

For example, the article can be a fabric or the article can be a ware.

Also disclosed herein are methods of cleaning a membrane. The methodscomprise contacting the membrane with a cleaning composition comprisingthe compound of Formula 1, 2, or 3 as described herein.

The membrane can be a membrane used in a dairy process.

The membrane can be a microfiltration membrane, an ultrafiltrationmembrane, a nanofiltration membrane, a reverse osmosis membrane, or acombination thereof.

Other objects and features will be in part apparent and in part pointedout hereinafter.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIG. 1 is a gas chromatography-mass spectra (GC-MS) profile of thereaction mixture of Example 1.

FIG. 2 is a ¹H NMR for the product of Example 1.

FIG. 3 is a graph of the torque versus time for various activators andactivator blends as described in Example 3A.

FIG. 4 is a graph of the torque versus time for various activators andactivator blends as described in Example 3B.

FIG. 5 is a graph of the torque versus time for various activators andactivator blends as described in Example 3C.

FIG. 6 is a graph of the torque versus time for various activators andactivator blends as described in Example 4A.

FIG. 7 is a graph of the torque versus time for various activators andactivator blends as described in Example 4B.

FIG. 8 is a graph of the torque versus time for various activators andactivator blends as described in Example 5A.

FIG. 9 is a graph of the torque versus time for various activators andactivator blends as described in Example 5B.

FIG. 10 is a graph of the torque versus time for various activators andactivator blends as described in Example 6.

FIGS. 11A, 11B, and 11C are graphs of the % soil removed from couponsfor various surfactant compositions as described in Example 10.

FIG. 12 is a graph plotting the contact angle over time for waterdroplets with or without the surfactant compositions as described inExample 11.

FIG. 13 is a graph of the % soil removed from coupons for varioussurfactant compositions as described in Example 12.

FIGS. 14A and 14B are graphs of the foam height for particularsurfactant compositions as described in Example 13.

FIGS. 15A and 15B are graphs of the foam height over time for thesurfactant compositions as described in Example 14.

Corresponding reference characters indicate corresponding partsthroughout the drawings.

DETAILED DESCRIPTION OF THE INVENTION

Compounds and compositions are provided that can dissolve water-solubleor water-dispersible polymers rapidly and completely in aqueoussolution. The polymer compositions containing the surfactant compoundsand compositions described herein can be used in various industriesincluding for water clarification, papermaking, sewage and industrialwater treatment, drilling mud stabilizers, and enhanced oil recovery.The compounds and compositions herein can also be used as generalsurfactants in detergent compositions or in methods of cleaning articlesor membranes.

Polymer compositions including water-in-oil emulsions and inversionsurfactants are provided. Also, methods of dissolving a water-soluble orwater-dispersible polymer are disclosed.

Therefore, polymer compositions and methods using the polymercompositions are described herein. Disclosed herein are compounds andcompositions useful as inversion surfactants and to aid in thedissolution of polymers. Also provided are detergent and cleaningcompositions comprising the compounds and methods of cleaning articlesor membranes. For example, disclosed herein is the compound of Formula 1having the structure of Formula 1:

wherein A is an optionally substituted phenyl, naphthalene, indole,purine, pyridine, quinoline, isoquinoline, pyrimidine, pyrole, furan,thiophene, imidazole, or thiazole; and Z has a structure of moiety A ormoiety B:

wherein Xis —O—, —N(R₁₀)—, —OC(O)—, —C(O)O—, —N(R₁₀)C(O)—, —C(O)N(R₁₀)—,—OC(O)O—, —OC(O)N(R₁₀)—N(R₁₀)C(O)O—, or —N(R₁₀)C(O) N(R₁₀)—; n is aninteger from 0 to 10; R₆ and R₉ are independently hydrogen, alkyl, oraryl; R₇ is alkyl, aryl, or —(CH₂)z-O—R₁₁, R₈ is independently hydrogen,alkyl, or aryl; R₁₀ is hydrogen, alkyl, or Z; R₁₁ is hydrogen or alkyl;m is independently an integer from 3 to 20; and z is an integer from 1to 10.

The compounds of Formula 1 can have moiety B have the structure ofmoiety B1 or moiety B2:

wherein R₉ is independently hydrogen, alkyl, or aryl; and R₁₂ isindependently C₃ to C₂₂ alkyl or alkenyl.

The compounds of Formula 1 can have A be an optionally substitutedphenyl, naphthyl, pyridyl, quinolyl, or isoquinolyl.

The compounds of Formula 1 can have A be an optionally substitutedphenyl or naphthyl.

Further, the compounds can have the structure of Formula 2:

wherein R₁, R₂, R₃, R₄, and R₅ are independently hydrogen, Z, alkyl,alkoxyl, or two adjacent R groups combine to form a fused ring; Z has astructure of moiety A or moiety B:

wherein Xis —O—, —N(R₁₀)—, —OC(O)—, —C(O)O—, —N(R₁₀)C(O)—, —C(O)N(R₁₀)—,—OC(O)O—, —OC(O)N(R₁₀)—N(R₁₀)C(O)O—, or —N(R₁₀)C(O) N(R₁₀)—; n is aninteger from 0 to 10; R₆ and R₉ are independently hydrogen, alkyl, oraryl; R₇ is alkyl, aryl, or —(CH₂)z-O—R₁₁, R₈ is independently hydrogen,alkyl, or aryl; R₁₀ is hydrogen, alkyl, or Z; R₁₁ is hydrogen or alkyl;m is an integer from 3 to 20; and z is an integer from 1 to 10.

The compounds of Formula 2 can have moiety B have the structure ofmoiety B1 or moiety B2:

wherein R₉ is independently hydrogen, alkyl, or aryl; and R₁₂ isindependently C₃ to C₂₂ alkyl or alkenyl.

The compounds of Formula 2 can have at least one of R₁, R₂, R₃, R₄, andR₅ be Z.

The compounds of Formula 2 can have Z have the structure of moiety A, Xbe —O—; n be 0; R₁, R₂, R₃, R₄, R₅ be hydrogen; R₇ be —(CH₂)z-O—R₁₁, zbe 1, R₈ be hydrogen, R₁₁ be 2-ethylhexyl, and m be an integer from 7 to13 or an integer from 7 to 12.

The compounds can have the structure of Formula 3:

wherein R₁, R₂, R₄, and R₅ are independently hydrogen, alkyl, alkoxyl,or Z; and Z₁, Z₂, and Z independently have a structure of moiety A ormoiety B:

wherein X is —O— or —N(R₁₀)—; n is an integer from 0 to 5; R₆ and R₉ areindependently hydrogen or alkyl; R₇ is alkyl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₀ is hydrogen, alkyl, or Z;R₁₁ is hydrogen or alkyl; m is an integer from 3 to 20; and z is aninteger from 1 to 10.

The compounds of Formula 1 or 2 can have R₁, R₂, R₃, R₄, and R₅independently be hydrogen or C₁ to C₄ alkyl.

The compounds of Formula 1 or 2 can have R₁, R₂, R₃, R₄, and R₅ behydrogen.

The compounds of Formula 1, 2, or 3 can have R₆ and R₉ be hydrogen.

The compounds of Formula 1, 2, or 3 can have R₈ be hydrogen or methyl.

The compounds Formula 1, 2, or 3 can have R₇ be —(CH₂)z-O—R₁₁.

The compounds of Formula 1, 2, or 3 can have z be 1 to 3.

The compounds of Formula 1, 2, or 3 can have R₁₁ be C₄ to C₂₂ alkyl.

The compounds of Formula 1, 2, or 3 can have X be —O— or —N(R₁₀)—.

The compounds of Formula 1, 2, or 3 can have X be —O—.

The compounds of Formula 1, 2, or 3 can have X be —N(R₁₀)—.

The compounds of Formula 1, 2, or 3 can have R₁₀ be hydrogen.

The compounds can have the structures:

The compounds can also have a structure of Formula 4:

wherein R₁, R₂, R₄, and R₅ are independently hydrogen, alkyl, oralkoxyl; Z₁ is has a structure of moiety C

Z₂ has a structure of moiety D

n is an integer from 0 to 5; R₇ is alkyl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₁ is hydrogen or alkyl; m isan integer from 3 to 30; and z is an integer from 0 to 6.

The compounds having a structure of Formula 4 can have n be 0.

The compounds having a structure of Formula 4 can have R₇ be—(CH₂)z-O—R₁₁, and z be 1.

The compounds having a structure of Formula 4 can have R₈ be hydrogen.

The compounds having a structure of Formula 4 can have R₁₁ be2-ethylhexyl.

The compounds having a structure of Formula 4 can have m be an integerfrom 10 to 30.

The compounds having a structure of Formula 4 can have R₁, R₂, R₄, andR₅ be hydrogen or methyl; preferably, R₁, R₂, R₄, and R₅ are hydrogen.

The compounds of Formula 4 can have the following structure

wherein o, p, and q are integers and sum of o, p and q is 10, 12, 14,16, 18, 20, 22, or 24.

Polymer compositions described herein can comprise a water-in-oilemulsion comprising an aqueous phase comprising water and awater-soluble or water-dispersible polymer, and an oil phase comprisingan oil and an emulsifying agent; and an inversion surfactant comprisingthe compound of Formula 1, 2, 3, or 4 described herein.

The polymer compositions described herein can have the water-in-oilemulsion further comprise the inversion surfactant.

The polymer compositions can further comprise an aqueous solutioncontaining the inversion surfactant.

A polymer composition can also comprise a water-soluble orwater-dispersible polymer, an oil, a suspending agent, and the inversionsurfactant comprising a compound of Formula 1, 2, 3, or 4 describedherein.

Disclosed herein are also methods of dissolving the water-soluble orwater-dispersible polymer of the polymer compositions disclosed herein.The method comprising contacting the water-in-oil emulsion with theinversion surfactant.

The methods disclosed herein can have the water-in-oil emulsion furthercomprise the inversion surfactant and the water-in-oil emulsion iscontacted with an aqueous solution.

The methods can have the water-in-oil emulsion be contacted with anaqueous solution comprising the inversion surfactant.

The polymer compositions or methods can have the inversion surfactanthave a concentration of from about 0.1 wt. % to about 10 wt. % based onthe total weight of the emulsion.

The polymer compositions or methods disclosed herein can have theinversion surfactant have a concentration of from about 0.5 wt. % toabout 5 wt. % based on the total weight of the emulsion.

The polymer compositions or methods can have the polymer compositionsfurther comprise an ethoxylated C₁₀-C₁₆ alcohol; a C₁₂-C₁₃ primaryalcohol of linear and mono-methyl branched alcohol having on average 9moles ethylene oxide; an ethoxylate of a saturated C₁₂-15 alcohol; anethoxylated C₁₂-14 alcohol; an ethoxylated primary branched saturatedC₁₃ alcohol; an ethoxylated C₁₀ Guerbet alcohol; an ethoxylatedsaturated iso-C₁₃ alcohol; a saturated, predominantly unbranched C₁₃-15oxo alcohol having 11 ethylene oxide groups; a secondary alcoholethoxylate; a nonionic, alkoxylated alcohol; a polyoxyethylene (9)synthetic primary C₁₃/C₁₅ alcohol; an isotridecyl alcohol ethoxylatedwith an average of 9 moles ethylene oxide; an ethoxylated linear primaryC₁₂-14 alcohol; an ethoxylated nonylphenol;tert-octylphenoxypoly(ethoxyethanol); a tridecyl ether phosphate; apolyoxyethylene (5) soyaallylamine; a polyethylene glycol (PEG) 400monooleate; a PEG 600 monooleate; aPEG-25 castor oil; a PEG-30 castoroil; a PEG-40 castor oil; an aliphatic phosphate ester with 10 moles EO;an aliphatic phosphate ester with 6 moles EO; an oleic acid monoethanolamide with 14 moles ethylene oxide; a soyamine ethoxylate; or acombination thereof.

The methods described herein can have the inversion surfactant beactivated by contacting the inversion surfactant with an aqueoussolution.

The methods disclosed herein can have the inversion surfactant beactivated by contacting the inversion surfactant with an inversion aid.

The methods can also have the inversion aid comprise glycol, apolypropylene glycol, polyglycerol, urea, sorbitol, sucrose, glycerol, apolyglycerol, a phosphate, choline chlorine, guanidine,dioctyl-sulfosuccinate, malic acid, lactic acid,N-(phosphonomethyl)glycine, 2-phosphonopropanoic acid,3-phosphonopropanoic acid, 4-phosphonobutanoic acid, a phosphinosuccinicoligomer, a polyethylene glycol, urea, sorbitol, sucrose, glycerol, aphosphate, choline chlorine, or a combination thereof.

The methods can further have the aqueous solution contain a salt.

The methods can also have the temperature of the aqueous solution beincreased from about 2° C. to about 65° C.

The polymer composition can comprise from about 5 wt. % to about 70 wt.%, from about 10 wt. % to about 70 wt. %, from about 20 wt. % to about70 wt. %, from about 30 wt. % to about 70 wt. %, from about 40 wt. % toabout 70 wt. %, from about 50 wt. % to about 70 wt. %, from about 60 wt.% to about 70 wt. %, from about 10 wt. % to about 60 wt. %, from about10 wt. % to about 50 wt. %, from about 15 wt. % to about 70 wt. %, fromabout 15 wt. % to about 65 wt. %, from about 18 wt. % to about 65 wt. %,from about 20 wt. % to about 60 wt. %, from about 20 wt. % to about 50wt. %, from about 25 wt. % to about 70 wt. %, from about 25 wt. % toabout 60 wt. %, from about 25 wt. % to about 50 wt. %, of thewater-soluble or water-dispersible polymer. Preferably, the polymercomposition comprises from about 18 wt. % to about 65 wt. % of thewater-soluble or water-dispersible polymer.

The polymer composition can be a slurry comprising a water-solublepolymer suspended in an oil-based vehicle with a suspension agent and aninversion surfactant comprising a compound of Formula 1, 2, or 3.

Specifically, the oil-based vehicle can be petroleum distillate.Petroleum distillates are products distilled from petroleum crude oiland use different CAS #identifiers depending upon the molecular weightdistribution and processing technology used. A petroleum distillatesuitable for the present composition can be, for example, CAS#64742-47-8.

The suspension aid can be a variation of diblock copolymers based onstyrene and ethylene/propylene. The composition can also contain adispersant such as organophilic clay or a synthetic alternative as thesuspension agent.

The inversion surfactant comprising a compound having the structure ofFormula 1, 2, or 3 can be blended with one or more additional inversionsurfactants. For example, the additional inversion surfactants ofinterest having HLBs from about 9 to about 15 include those listed inthe following table and combinations thereof.

Trade Name Chemistry Alfonic 1412-7 Ethoxylated C₁₀-C₁₆ alcohols Novel23E9 C₁₂-C₁₃ primary alcohol of linear and mono-methyl branched alcoholshaving on average 9 moles EO Synperonic A11 Ethoxylate of a saturatedC₁₂₋₁₅ alcohol Surfonic 1412-12 Ethoxylated C₁₂₋₁₄ alcohol Synperonic13/7 Ethoxylated primary branched saturated C₁₃ alcohol Lutensol TO10Ethoxylated C₁₀ Guerbet alcohol Lutensol TO12 Ethoxylated saturatediso-C₁₃ alcohol Lutensol AO11 Saturated, predominantly unbranched C₁₃₋₁₅oxo alcohols having 11 EO groups Tergitol 15-S-9 Secondary AlcoholEthoxylate Tergitol 15-S-12 Secondary Alcohol Ethoxylate Plurafac RA 20Nonionic, alkoxylated alcohol Plurafac RA 30 Nonionic, alkoxylatedalcohol Synperonic A9 Polyoxyethylene (9) synthetic primary C₁₃/C₁₅alcohol Alfonic TDA9 Isotridecyl alcohol ethoxylated with an average of9 moles EO Novel 1412-11 Ethoxylated linear primary C₁₂₋₁₄ alcoholTergitol NP-9.5 Ethoxylated nonylphenol Tergitol NP-10.5 Ethoxylatednonylphenol Triton X-114 tert-octylphenoxypoly(ethoxyethanol) RhodafacRS-410 Tridecyl ether phosphate Ethomeen S/15 Polyoxyethylene (5)soyaallylamines Ethox MO-9 PEG 400 monooleate Ethox MO-14 PEG 600monooleate Ethox CO-25 PEG-25 Castor oil Alkamul EL-620 PEG-30 Castoroil Ethox CO-40 PEG-40 Castor oil Rhodafac RS-710 Aliphatic phosphateester, 10 moles EO Rhodafac RS-610 Aliphatic phosphate ester, 6 moles EOSerdox NXC-14 Oleic acid monoethanol amide + 14 EO Ethomeen S/25Soyamine ethoxylate

The inversion surfactant comprising a compound having the structure ofFormula 1, 2, or 3 can be blended with an ethoxylated C₁₀-C₁₆ alcohol; aC₁₂-C₁₃ primary alcohol of linear and mono-methyl branched alcoholhaving on average 9 moles ethylene oxide; an ethoxylate of a saturatedC₁₂-15 alcohol; an ethoxylated C₁₂-14 alcohol; an ethoxylated primarybranched saturated C₁₃ alcohol; an ethoxylated C₁₀ Guerbet alcohol; anethoxylated saturated iso-C₁₃ alcohol; a saturated, predominantlyunbranched C₁₃-15 oxo alcohol having 11 ethylene oxide groups; asecondary alcohol ethoxylate; a nonionic, alkoxylated alcohol; apolyoxyethylene (9) synthetic primary C₁₃/C₁₅ alcohol; an isotridecylalcohol ethoxylated with an average of 9 moles ethylene oxide; anethoxylated linear primary C₁₂₋₁₄ alcohol; an ethoxylated nonylphenol;tert-octylphenoxypoly(ethoxyethanol); a tridecyl ether phosphate; apolyoxyethylene (5) soyaallylamine; a polyethylene glycol (PEG) 400monooleate; a PEG 600 monooleate; aPEG-25 castor oil; a PEG-30 castoroil; a PEG-40 castor oil; an aliphatic phosphate ester with 10 moles EO;an aliphatic phosphate ester with 6 moles EO; an oleic acid monoethanolamide with 14 moles ethylene oxide; a soyamine ethoxylate; or acombination thereof.

Also disclosed are methods of preparing a compound described herein, themethod comprising reacting compound (A) with compound (B) to formcompound (C); and further reacting compound (C) with compound (D) toform compound (E)

wherein A, X, R₆, R₇, R₈, R₉, n and m are as defined in connection withthe compounds herein above.

Another method of preparing a compound described herein comprisesreacting compound (F) with R—XH and an acid catalyst to form compound(G); and further reacting compound (G) with compound (D) to formcompound (H); or

reacting compound (F) with R—XH and a base catalyst to form compound(J); and further reacting compound (J) with compound (D) to formcompound (K);

wherein A, X, R₆, R₇, R₈, R₉, n and m are as defined in connection withthe compounds herein; and R is independently hydrogen or alkyl.

The compounds having the structure of Formula 1, 2, or 3 can be preparedby the following synthetic schemes:

wherein A, X, R₆, R₇, R₈, m, and n are defined as above.

wherein A, X, m, and n are defined as above, and R is independentlyhydrogen or alkyl.

In the described polymer composition, the inversion surfactantcomprising a compound having the structure of Formula 1, 2, or 3 canhave a concentration of from about 0.1 wt. % to about 10 wt. % based onthe total weight of the polymer composition. Preferably, the inversionsurfactant comprising a compound having the structure of Formula 1, 2,or 3 has a concentration of from about 0.5 wt. % to about 5 wt. % basedon the total weight of the polymer composition.

The water-in-oil polymer emulsion can further comprise an emulsifyingagent. The surfactant or blend of surfactants can have a lowhydrophile-lipophile balance (HLB) to aid preparation of anoil-continuous emulsion. Appropriate surfactants for water-in-oilemulsion polymerizations which are commercially available are compiledin the North American Edition of McCutcheon's Emulsifiers & Detergents.For example, the emulsifying agent can comprise nonionic ethoxylatedfatty acid esters, ethoxylated sorbitan fatty acid esters, sorbitanesters of fatty acids such as sorbitan monolaurate, sorbitanmonostearate, and sorbitan monooleate, block copolymers of ethyleneoxide and hydroxyacids having a C₁₀-C₃₀ linear or branched hydrocarbonchain, linear or branched alcohol alkoxylates, or a combination thereof.

The emulsifying agent can be a single nonionic surfactant or blendthereof having a combined HLB value of about 2 to 10, for example about3 to 10, or about 4 to 10, or about 5 to 10, or about 6 to 10, or about7 to 10, or about 8 to 10, or about 2 to 9, or about 2 to 8, or about 2to 7, or about 2 to 6, or about 2 to 5, or about 3 to 9, or about 4 to8.

The water-in-oil emulsion can also comprise an alcohol alkoxylate. Thealcohol alkoxylate can comprise a linear or branched alcohol ethoxylate,or a combination thereof.

The surfactant compositions, as described above, are useful as inverters(activators) of water-in-oil (inverse) emulsion polymers in variousindustries including for water clarification, papermaking, sewage andindustrial water treatment, drilling mud stabilizers, and enhanced oilrecovery.

The water-soluble or water-dispersible polymers useful in the polymercompositions include various polymers and their mixtures, orderivatives. The water-soluble or water-dispersible polymers used can bean anionic, a cationic, a nonionic, a zwitterionic, or an amphotericpolymer.

For example, the water-soluble or water-dispersible polymers containedin the polymer compositions can comprise polyacrylamides, polyacrylates,copolymers thereof, and hydrophobically modified derivatives of thesepolymers.

Further, the water-soluble or water-dispersible polymers used in thepolymer compositions described herein can include the water-soluble orwater-dispersible polymers described in U.S. Pat. Nos. 3,624,019 and3,734,873; the water-soluble or water-dispersible polymers can havevarious architectures as disclosed in EP 202780 (linear andcross-linked), and EP 374458, U.S. Pat. Nos. 5,945,494 and 5,961,840(branched). Additionally, the water-soluble or water-dispersiblepolymers can contain hydrophobic monomers as disclosed in U.S. Pat. No.4,918,123. These references are herein incorporated by reference fortheir various disclosures of water-soluble and water-dispersiblepolymers.

The polymers usefully incorporated in the polymer compositions typicallyhave a weight average molecular weight (MW) of about 500,000 Daltons toabout 100,000,000 Daltons, or about 1,000,000 Daltons to about50,000,000 Daltons, or about 5,000,000 Daltons to about 30,000,000Daltons.

The water-soluble or water-dispersible polymer can comprise about 1 mol% to about 100 mol % acrylamide monomers, or about 1 mol % to about 90mol %, or about 1 mol % to about 80 mol %, or about 1 mol % to about 70mol %, or about 1 mol % to about 60 mol %, or about 1 mol % to about 50mol %, or about 1 mol % to about 40 mol %, or about 1 mol % to about 30mol %, or about 1 mol % to about 20 mol %, or about 1 mol % to about 10mol %, or about 10 mol % to about 100 mol %, or about 20 mol % to about100 mol %, or about 30 mol % to about 100 mol %, or about 40 mol % toabout 100 mol %, or about 50 mol % to about 100 mol %, or about 60 mol %to about 100 mol %, or about 70 mol % to about 100 mol %, or about 80mol % to about 100 mol %, or about 90 mol % to about 100 mol %, or about20 mol % to about 80 mol, or about 30 mol % to about 70 mol %, or about40 mol % to about 60 mol %, or about 60 mol % to about 80 mol %acrylamide monomers.

The water-soluble polymer or water-dispersible polymer can be presentwithin the water-in-oil emulsion at about 15 wt % to 70 wt %, or about17 wt % to 70 wt %, or about 19 wt % to 70 wt %, or about 21 wt % to 70wt %, or about 23 wt % to 70 wt %, or about 25 wt % to 70 wt %, or about15 wt % to 68 wt %, or about 15 wt % to 66 wt %, or about 15 wt % to 64wt %, or about 15 wt % to 62 wt %, or about 15 wt % to 60 wt %, or about15 wt % to 58 wt %, or about 15 wt % to 56 wt %, or about 25 wt % to 65wt %, or about 30 wt % to 60 wt %, or about 30 wt % to 60 wt % based onthe total weight of the emulsion.

Inverse emulsion polymers are prepared by dissolving the requiredmonomers in the water phase, dissolving the emulsifying agent in the oilphase, emulsifying the water phase in the oil phase to prepare awater-in-oil emulsion, homogenizing the water-in-oil emulsion andpolymerizing the monomers to obtain the polymer. A self-invertingsurfactant may be added to the water-soluble polymer dispersed withinthe hydrocarbon matrix to obtain a self-inverting water-in-oil emulsion.Alternatively, a polymer solution can be made-up by inverting thepolymer dispersed in oil in to water containing the surfactant.

Also present in the water-in-oil emulsion is an amount of watersufficient to form an aqueous (i.e. water) phase within the emulsion.Water is present in the water-in-oil emulsion at about 3 wt % to 50 wt%, or about 5 wt % to 50 wt %, or about 10 wt % to 50 wt %, or about 15wt % to 50 wt %, or about 20 wt % to 50 wt %, or about 25 wt % to 50 wt%, or about 3 wt % to 35 wt %, or about 3 wt % to 30 wt %, or about 3 wt% to 25 wt %, or about 5 wt % to 45 wt %, or about 5 wt % to 40 wt %, orabout 5 wt % to 35 wt %, based on the total weight of the water-in-oilemulsion.

The water-in-oil emulsion also contains an amount of oil sufficient toform an oil phase within the water-in-oil emulsion.

The oil in the oil phase can be a mixture of compounds, wherein themixture is less than 0.1 wt % soluble in water at 25° C. and is a liquidover the range of 20° C. to 90° C.

The oil in the oil phase can comprise a linear, branched, or cyclichydrocarbon moieties, aryl or alkaryl moieties, or combinations thereof.

The oil in the oil phase can have a density of about 0.8 g/L to 1.0 g/L,for example about 0.8 g/L to 0.9 g/L.

Examples of suitable oils for the oil phase can include a petroleumdistillate, decane, dodecane, isotridecane, cyclohexane, toluene,xylene, and mixed paraffin solvents such as those sold under the tradename ISOPAR® by ExxonMobil Corp. of Irving, Tex.

The oil phase is present in the water-in-oil emulsion at about 10 wt %to 40 wt %, or about 15 wt % to 40 wt %, or about 20 wt % to 40 wt %, orabout 22 wt % to 40 wt %, or about 24 wt % to 40 wt %, or about 26 wt %to 40 wt %, or about 28 wt % to 40 wt %, or about 30 wt % to 40 wt %, orabout 10 wt % to 38 wt %, or about 10 wt % to 36 wt %, or about 10 wt %to 34 wt %, or about 10 wt % to 32 wt %, or about 10 wt % to 30 wt %, orabout 10 wt % to 25 wt %, or about 10 wt % to 20 wt %, or about 15 wt %to 35 wt %, or about 20 wt % to 30 wt % based on the total weight of thewater-in-oil emulsion.

The inversion surfactant comprising compounds of Formula 1, 2, or 3 aidsthe inversion of the water-in-oil emulsion compared to a water-in-oilemulsion comprising no inversion surfactant or compared to awater-in-oil emulsion comprising a comparator inversion surfactant. Theinversion surfactant comprising a compound of Formula 1, 2, or 3increases the speed and/or percent completion of the inversion processcompared to a water-in-oil emulsion comprising no inversion surfactantor compared to a water-in-oil emulsion comprising a comparator inversionsurfactant.

To aid inversion of a water-in-oil emulsion, the inversion surfactantcomprising a compound of Formula 1, 2, or 3 is added to the emulsion atabout 0.1 wt % to 20.0 wt % based on the total weight of the emulsion,or about 0.1 wt % to 15.0 wt %, or about 0.1 wt % to 10.0 wt %, or about0.1 wt % to 7.5 wt %, or about 0.1 wt % to 5.0 wt %, or about 0.5 wt %to 4.5 wt %, or about 1.0 wt % to 4.0 wt %, or about 1.5 wt % to 3.5 wt%, or about 2.0 wt % to 3.0 wt %, or about 0.1 wt % to 4.5 wt %, orabout 0.1 wt % to 4.0 wt %, or about 0.1 wt % to 3.5 wt %, or about 0.1wt % to 3.0 wt %, or about 0.5 wt % to 5.0 wt %, or about 1.0 wt % to5.0 wt %, or about 1.5 wt % to 5.0 wt %, or about 2.0 wt % to 5.0 wt %,based on the total weight of the emulsion.

The inversion surfactant can be added to the aqueous solution contactedwith the emulsion to activate the polymer in a concentration of about0.1 wt % to 20.0 wt % based on the total weight of the aqueous solution,or about 0.1 wt % to 15.0 wt %, or about 0.1 wt % to 10.0 wt %, or about0.1 wt % to 7.5 wt %, or about 0.1 wt % to 5.0 wt %, or about 0.5 wt %to 4.5 wt %, or about 1.0 wt % to 4.0 wt %, or about 1.5 wt % to 3.5 wt%, or about 2.0 wt % to 3.0 wt %, or about 0.1 wt % to 4.5 wt %, orabout 0.1 wt % to 4.0 wt %, or about 0.1 wt % to 3.5 wt %, or about 0.1wt % to 3.0 wt %, or about 0.5 wt % to 5.0 wt %, or about 1.0 wt % to5.0 wt %, or about 1.5 wt % to 5.0 wt %, or about 2.0 wt % to 5.0 wt %,based on the total weight of the aqueous solution.

The effective amount of the polymer composition can be from about 1 ppmto about 10000 ppm, from about 1 ppm to about 9000 ppm, from about 1 ppmto about 8000 ppm, from about 1 ppm to about 7000 ppm, from about 1 ppmto about 6000 ppm, from about 1 ppm to about 5000 ppm, from about 1 ppmto about 4000 ppm, from about 1 ppm to about 3000 ppm, from about 1 ppmto about 2000 ppm, from about 1 ppm to about 1000 ppm, based on thetotal weight of the process fluid. Preferably, the effective amount ofthe polymer composition is from about 1 ppm to about 900 ppm, from about1 ppm, to about 800 ppm, from about 1 ppm to about 700 ppm, from about 1ppm to about 600 ppm, or from about 1 ppm to about 500 ppm. Further, theeffective amount of the polymer composition can be from about 1 ppm toabout 250 ppm, from about 1 ppm to about 200 ppm, from about 1 ppm toabout 100 ppm, from about 1 ppm to about 75 ppm, from about 1 ppm toabout 50 ppm, from about 1 ppm to about 25 ppm, from about 1 ppm toabout 15 ppm, or from about 1 ppm to about 10 ppm, based on the totalweight of the process fluid.

The inversion and dilution to a target concentration of less than 1 wt %can be accomplished in about 1 to 15 minutes, for example about 1 to 14,1 to 13, 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to5, 2 to 15, 3 to 15, 4 to 15, 5 to 15, 6 to 15, 7 to 15, 8 to 15, 9 to15, 10 to 15, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, or 2 to 5minutes.

After inversion, the aqueous solutions can comprise about 100 ppm to10,000 ppm (0.01 wt % to 1.00 wt %) water-soluble or water-dispersiblepolymer, or about 200 ppm to 5000 ppm, or about 200 ppm to 4000 ppm, orabout 200 ppm to 3000 ppm, or about 200 ppm to 2500 ppm water-soluble orwater-dispersible polymer, based on the total weight of the aqueoussolution.

Compositions

The compounds described herein are also useful as general surfactants,e.g., for use in detergents or cleaning solutions.

Exemplary cleaning or detergent compositions include, but are notlimited to dishwashing detergents, rinse aids, floor cleaners, presoaks,manual cleaners, degreasers, hard surface cleaners, laundry detergents,sanitizers, disinfectants, food and beverage equipment cleaners, anddairy cleaners. Cleaning compositions and detergent compositionscomprising a compound of formula 1, 2 or 3, as described herein, areprovided. These compositions can be used for a variety of cleaningapplications as described above, but are particularly useful asdetergents or membrane cleaners.

The cleaning and/or detergent compositions described herein may comprisea compound of formula 1, 2, or 3 as described herein and at least one ofa builder, a chelating agent, a scale inhibitor, a surfactant or anycombination thereof.

The detergent and/or cleaning compositions can comprise from about 0.001to about 99 wt. %, of the compound of Formula 1, 2, or 3, based on thetotal weight of the detergent and/or cleaning composition as describedherein.

Building Agents

Therefore, a cleaning composition or a detergent composition is providedcomprising a building agent and a compound of Formula 1, 2, or 3 asdescribed herein.

The detergent composition or cleaning composition can comprise fromabout 0.1 to about 90 wt. %, of the building agent, based on the totalweight of the detergent composition or the cleaning composition.

Examples of suitable building agents include, but are not limited toalkali metal carbonates, alkali metal hydroxides, and alkali metalsilicates. Exemplary alkali metal carbonates that can be used include,but are not limited to: sodium or potassium carbonate, bicarbonate,sesquicarbonate, and mixtures thereof. Exemplary alkali metal hydroxidesthat can be used include, but are not limited to: sodium or potassiumhydroxide. The alkali metal hydroxide may be added to the composition inany form known in the art, including as solid beads, dissolved in anaqueous solution, or a combination thereof. Examples of alkali metalsilicates include, but are not limited to sodium or potassium silicateor polysilicate, sodium or potassium metasilicate and hydrated sodium orpotassium metasilicate or a combination thereof.

The building agent can comprise an alkaline detergent builder. Forexample, the building agent can comprise an enzyme, an oxidizing agent,a condensed phosphate, an alkali metal carbonate, an alkali metalsilicate, an alkali metal metasilicate, a phosphonate, an aminocarboxylic acid, a carboxylic acid polymer, or a combination thereof.The detergent composition or cleaning composition can further comprisechelants, surfactants, enzymes, or other components as described hereinbelow.

Chelants

The cleaning composition or detergent composition disclosed herein mayalso comprise a chelant. Chelants include, but are not limited to,chelating agents (chelators), sequestering agents (sequestrants), andthe like. Examples of chelants include, but are not limited to,phosphonates, phosphates, aminocarboxylates and their derivatives,pyrophosphates, polyphosphates, ethylenediamine and ethylenetriaminederivatives, hydroxyacids, and mono-, di-, and tri-carboxylates andtheir corresponding acids. Other exemplary chelants includealuminosilicates, nitroloacetates and their derivatives, and mixturesthereof.

Suitable aminocarboxylic acids according to the invention include, butare not limited to, methylglycinediacetic acid (MGDA), glutamicacid-N,N-diacetic acid (GLDA), N-hydroxyethylaminodiacetic acid,ethylenediaminetetraacetic acid (EDTA) (including tetra sodium EDTA),hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), ethylenediaminesuccinic acid(EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid(IDS), 3-hydroxy-2-2′-iminodisuccinic acid (HIDS) and other similaracids or salts thereof having an amino group with a carboxylic acidsubstituent. Additional description of suitable aminocarboxylatessuitable for use as chelating agents and/or sequestrants is set forth inKirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume5, pages 339-366 and volume 23, pages 319-320, the disclosure of whichis incorporated by reference herein.

Chelants can be water soluble, and/or biodegradable. Other exemplarychelants include TKPP (tetrapotassium pyrophosphate), PAA (polyacrylicacid) and its salts, phosphonobutane carboxylic acid,Alanine,N,N-bis(carboxymethyl)-,trisodium salt, and sodium gluconate.

The chelant can be free of phosphorus. The chelant may also serve as asolidifying agent to help form the solid composition, such as sodiumsalts of citric acid.

Preferably, the chelant is a sodium salt of aminocarboxylates. Morepreferably, the chelant is methyl glycine diacetic acid (MGDA).

Alternatively, the cleaning composition or detergent compositiondisclosed herein can be free of a chelant, detergent builder, or both.Alternatively, the cleaning composition or detergent compositiondisclosed herein can be free of a chelant, detergent builder, or boththat contain phosphorus.

Scale Inhibitors

The cleaning composition or detergent composition can further compriseone or more scale inhibitors. Suitable scale inhibitors include, but arenot limited to, phosphates, phosphate esters, phosphoric acids,phosphonates, phosphonic acids, polyacrylamides, salts ofacrylamidomethyl propane sulfonate/acrylic acid copolymer (AMPS/AA),phosphinated maleic copolymer (PHOS/MA), mono-, bis- and oligomericphosphinosuccinic acid (PSO) derivatives, polycarboxylic acid,hydrophobically modified polycarboxylic acid, and salts of a polymaleicacid/acrylic acid/acrylamidomethyl propane sulfonate terpolymer(PMA/AA/AMPS). Suitable polycarboxylic acid polymers may comprise of oneor more monomers selected from the group consisting of acrylic acid,methacrylic acid, ethacrylic acid, maleic acid, maleic anhydride, anditaconic acid.

Alternatively, the cleaning composition or detergent compositiondisclosed herein can be free of a scale inhibitor.

Enzymes

The cleaning compositions or detergent compositions disclosed herein caninclude an enzyme. An enzyme in the cleaning compositions or detergentcompositions enhances removal of soils, prevents re-deposition, and/orreduces foam during applications of the cleaning compositions or theiruse solutions. The function of an enzyme is to break down adherentsoils, such as starch or proteinaceous materials, which are typicallyfound in soiled surfaces and removed by a cleaning composition ordetergent compositions into a wash water source.

Exemplary types of enzymes which can be incorporated into the cleaningcompositions or detergent compositions disclosed herein include, but arenot limited to, amylase, protease, lipase, cellulase, cutinase,gluconase, peroxidase, and/or mixtures thereof. A cleaning compositiondisclosed herein may employ more than one enzyme, from any suitableorigin, such as vegetable, animal, bacterial, fungal or yeast origin.The enzyme can be a protease. As used herein, the terms “protease” or“proteinase” refer enzymes that catalyze the hydrolysis of peptidebonds.

As understood by one skilled in the art, enzymes are designed to workwith specific types of soils. For example, ware wash applications mayuse a protease enzyme as it is effective at the high temperatures of theware wash machines and is effective in reducing protein-based soils.Protease enzymes are particularly advantageous for cleaning soilscontaining protein, such as blood, cutaneous scales, mucus, grass, food(e.g., egg, milk, spinach, meat residue, tomato sauce), or the like.Protease enzymes are capable of cleaving macromolecular protein links ofamino acid residues and convert substrates into small fragments that arereadily dissolved or dispersed into the aqueous use solution. Proteasesare often referred to as detersive enzymes due to the ability to breaksoils through the chemical reaction known as hydrolysis. Proteaseenzymes can be obtained, for example, from Bacillus subtilis, Bacilluslicheniformis and Streptomyces griseus. Protease enzymes are alsocommercially available as serine endoproteases.

Examples of commercially-available protease enzymes are available underthe following trade names: ESPERASE®, PURAFECT®, PURAFECT L®, PURAFECTOx®, EVERLASE®, LIQUANASE®, SAVINASE®, Prime L, Prosperase and BLAP.

The enzyme to be included into the cleaning composition may be anindependent entity and/or may be formulated in combination with thecleaning composition. For example, the enzyme may be formulated into acleaning composition in either liquid or solid formulations. Inaddition, enzyme compositions may be formulated into various delayed orcontrolled release formulations. For example, a solid molded cleaningcomposition may be prepared without the addition of heat. Enzymes candenature by heat so the use of enzymes within the cleaning compositionsmay require methods of forming cleaning compositions that do not relyupon heat as a step in the formation process, such as solidification.

The enzyme composition may be provided commercially in a solid (i.e.,puck, powder, etc.) or liquid formulation. Commercially-availableenzymes are generally combined with stabilizers, buffers, cofactors andinert vehicles. The actual active enzyme content depends upon the methodof manufacture, as is understood in the art.

Alternatively, the enzyme composition may be provided separate from thecleaning or detergent composition, and, for example, be added directlyto a use solution of a cleaning or detergent composition or a washliquor, or wash water of an application, e.g. dishwasher.

Surfactant

The cleaning composition or detergent composition can also comprise asurfactant. The surfactant can be an anionic, cationic, nonionic,amphoteric, zwitterionic, and/or gemini surfactant.

Anionic Surfactants

The cleaning composition or detergent composition can comprise ananionic surfactant. Anionic surfactants are surface active substances inwhich the charge on the hydrophobe is negative; or surfactants in whichthe hydrophobic section of the molecule carries no charge unless the pHis elevated to neutrality or above (e.g., carboxylic acids).Carboxylate, sulfonate, sulfate and phosphate are the polar(hydrophilic) solubilizing groups found in anionic surfactants. Of thecations (counter ions) associated with these polar groups, sodium,lithium and potassium impart water solubility; ammonium and substitutedammonium ions provide both water and oil solubility; and, calcium,barium, and magnesium promote oil solubility. As those skilled in theart understand, anionic surfactants are excellent detersive surfactantsand are therefore favored additions to heavy duty cleaning compositions.

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates),ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleicacid, and the like. Such carboxylates include alkyl ethoxy carboxylates,alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylatesurfactants and soaps (e.g., alkyl carboxyls). Secondary carboxylatesuseful in the present compositions include those which contain acarboxyl unit connected to a secondary carbon. The secondary carbon canbe in a ring structure, e.g., as in p-octyl benzoic acid, or as inalkyl-substituted cyclohexyl carboxylates. The secondary carboxylatesurfactants typically contain no ether linkages, no ester linkages andno hydroxyl groups. Further, they typically lack nitrogen atoms in thegroup-group (amphiphilic portion). Suitable secondary soap surfactantstypically contain 11-13 total carbon atoms, although more carbons atoms(e.g., up to 16) can be present. Suitable carboxylates also includeacylamino acids (and salts), such as acylgluamates, acyl peptides,sarcosinates (e.g., N-acyl sarcosinates), taurates (e.g., N-acyltaurates and fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X  (3)in which R is a C₈ to C₂₂ alkyl group or

in which R¹ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₈-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R¹ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R¹ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form. Commerciallyavailable carboxylates include: NEODOX 23-4, a C₁₂-C₁₃ alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and EMCOL CNP-110, a C₉ alkylarylpolyethoxy (10) carboxylic acid (Witco Chemical). Carboxylates are alsoavailable from Clariant, e.g., the product SANDOPAN DTC, a C₁₃ alkylpolyethoxy (7) carboxylic acid.

In some embodiments, the cleaning composition or detergent compositiondisclosed herein is free of an anionic surfactant.

Nonionic Surfactants

The cleaning composition or detergent composition can comprise anonionic surfactant.

Useful nonionic surfactants are generally characterized by the presenceof an organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants include block polyoxypropylene-polyoxyethylene polymericcompounds based upon propylene glycol, ethylene glycol, glycerol,trimethylolpropane, and ethylenediamine as the initiator reactivehydrogen compound. Examples of polymeric compounds made from asequential propoxylation and ethoxylation of initiator are commerciallyavailable from BASF Corp. One class of compounds are difunctional (tworeactive hydrogens) compounds formed by condensing ethylene oxide with ahydrophobic base formed by the addition of propylene oxide to the twohydroxyl groups of propylene glycol. This hydrophobic portion of themolecule weighs from about 1,000 to about 4,000. Ethylene oxide is thenadded to sandwich this hydrophobe between hydrophilic groups, controlledby length to constitute from about 10% by weight to about 80% by weightof the final molecule. Another class of compounds are tetra-functionalblock copolymers derived from the sequential addition of propylene oxideand ethylene oxide to ethylenediamine. The molecular weight of thepropylene oxide hydrotype ranges from about 500 to about 7,000; and, thehydrophile, ethylene oxide, is added to constitute from about 10% byweight to about 80% by weight of the molecule.

Suitable nonionic surfactants also include condensation products of onemole of alkyl phenol wherein the alkyl chain, of straight chain orbranched chain configuration, or of single or dual alkyl constituent,contains from about 8 to about 18 carbon atoms with from about 3 toabout 50 moles of ethylene oxide. The alkyl group can, for example, berepresented by diisobutylene, di-amyl, polymerized propylene, iso-octyl,nonyl, and di-nonyl. These surfactants can be polyethylene,polypropylene, and polybutylene oxide condensates of alkyl phenols.Examples of commercial compounds of this chemistry are available on themarket under the trade names IGEPAL® manufactured by Rhone-Poulenc andTRITON® manufactured by Union Carbide.

The nonionic surfactants can also be condensation products of one moleof a saturated or unsaturated, straight or branched chain alcohol havingfrom about 6 to about 24 carbon atoms with from about 3 to about 50moles of ethylene oxide. The alcohol moiety can consist of mixtures ofalcohols in the above delineated carbon range or it can consist of analcohol having a specific number of carbon atoms within this range.Examples of like commercial surfactant are available under the tradenames LUTENSOL™, DEHYDOL™ manufactured by BASF, NEODOL™ manufactured byShell Chemical Co. and ALFONIC™ manufactured by Vista Chemical Co.

Nonionic surfactants also include condensation products of one mole ofsaturated or unsaturated, straight or branched chain carboxylic acidhaving from about 8 to about 18 carbon atoms with from about 6 to about50 moles of ethylene oxide. The acid moiety can consist of mixtures ofacids in the above defined carbon atoms range or it can consist of anacid having a specific number of carbon atoms within the range. Examplesof commercial compounds of this chemistry are available on the marketunder the trade names DISPONIL or AGNIQUE manufactured by BASF andLIPOPEG™ manufactured by Lipo Chemicals, Inc.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances. Care must be exercised when adding these fatty estersor acylated carbohydrates to compositions of the present inventioncontaining amylase and/or lipase enzymes because of potentialincompatibility.

Examples of nonionic low foaming surfactants include, but are notlimited to, compounds which are modified, essentially reversed, byadding ethylene oxide to ethylene glycol to provide a hydrophile ofdesignated molecular weight; and, then adding propylene oxide to obtainhydrophobic blocks on the outside (ends) of the molecule. Thehydrophobic portion of the molecule weighs from about 1,000 to about3,100 with the central hydrophile including 10% by weight to about 80%by weight of the final molecule. These reverse Pluronics aremanufactured by BASF Corporation under the trade name PLURONIC™ Rsurfactants. Likewise, the TETRONIC™ R surfactants are produced by BASFCorporation by the sequential addition of ethylene oxide and propyleneoxide to ethylenediamine. The hydrophobic portion of the molecule weighsfrom about 2,100 to about 6,700 with the central hydrophile including10% by weight to 80% by weight of the final molecule.

Compounds which are modified by “capping” or “end blocking” the terminalhydroxy group or groups (of multi-functional moieties) to reduce foamingby reaction with a small hydrophobic molecule such as propylene oxide,butylene oxide, benzyl chloride; and, short chain fatty acids, alcoholsor alkyl halides containing from 1 to about 5 carbon atoms; and mixturesthereof. Also included are reactants such as thionyl chloride whichconvert terminal hydroxy groups to a chloride group. Such modificationsto the terminal hydroxy group may lead to all-block, block-heteric,heteric-block or all-heteric nonionics.

Additional examples of effective low foaming nonionic surfactantsinclude, but are not limited to:

-   -   (a) the alkylphenoxypolyethoxyalkanols of U.S. Pat. No.        2,903,486 issued Sep. 8, 1959 to Brown et al. and represented by        the formula

-   -   in which R is an alkyl group of 8 to 9 carbon atoms, A is an        alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to        16, and m is an integer of 1 to 10.    -   (b) The polyalkylene glycol condensates of U.S. Pat. No.        3,048,548 issued Aug. 7, 1962 to Martin et al. having alternated        hydrophilic oxyethylene chains and hydrophobic oxypropylene        chains where the weight of the terminal hydrophobic chains, the        weight of the middle hydrophobic unit and the weight of the        linking hydrophilic units each represent about one-third of the        condensate.    -   (c) The defoaming nonionic surfactants disclosed in U.S. Pat.        No. 3,382,178 issued May 7, 1968 to Lissant et al. having the        general formula Z[(OR)nOH]z wherein Z is alkoxylatable material,        R is a radical derived from an alkylene oxide which can be        ethylene and propylene and n is an integer from, for example, 10        to 2,000 or more and z is an integer determined by the number of        reactive oxyalkylatable groups.    -   (d) The conjugated polyoxyalkylene compounds described in U.S.        Pat. No. 2,677,700, issued May 4, 1954 to Jackson et al.        corresponding to the formula Y(C₃H₆O)_(n) (C₂H₄O)_(m)H wherein Y        is the residue of organic compound having from about 1 to 6        carbon atoms and one reactive hydrogen atom, n has an average        value of at least about 6.4, as determined by hydroxyl number        and m has a value such that the oxyethylene portion constitutes        about 10% to about 90% by weight of the molecule.    -   (e) The conjugated polyoxyalkylene compounds described in U.S.        Pat. No. 2,674,619, issued Apr. 6, 1954 to Lundsted et al.        having the formula Y[(C₃H₆O)_(n) (C₂H₄O)_(m)H]_(x) wherein Y is        the residue of an organic compound having from about 2 to 6        carbon atoms and containing x reactive hydrogen atoms in which x        has a value of at least about 2, n has a value such that the        molecular weight of the polyoxypropylene hydrophobic base is at        least about 900 and m has value such that the oxyethylene        content of the molecule is from about 10% to about 90% by        weight. Compounds falling within the scope of the definition for        Y include, for example, propylene glycol, glycerine,        pentaerythritol, trimethylolpropane, ethylenediamine and the        like. The oxypropylene chains optionally, but advantageously,        contain small amounts of ethylene oxide and the oxyethylene        chains also optionally, but advantageously, contain small        amounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n)(C₂H₄O)_(m)H]x wherein P is the residue of anorganic compound having from about 8 to 18 carbon atoms and containing xreactive hydrogen atoms in which x has a value of 1 or 2, n has a valuesuch that the molecular weight of the polyoxyethylene portion is atleast about 44 and m has a value such that the oxypropylene content ofthe molecule is from about 10% to about 90% by weight. In either casethe oxypropylene chains may contain optionally, but advantageously,small amounts of ethylene oxide and the oxyethylene chains may containalso optionally, but advantageously, small amounts of propylene oxide.

Polyhydroxy fatty acid amide surfactants suitable for use in the presentcompositions include those having the structural formula R²CONR¹Z inwhich: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,ethoxy, propoxy group, or a mixture thereof; R² is a C₅-C₃₁ hydrocarbyl,which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having alinear hydrocarbyl chain with at least 3 hydroxyls directly connected tothe chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z can be derived from a reducing sugar in areductive amination reaction; such as a glycityl moiety.

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 0 to about 25 moles of ethylene oxide are suitable for use inthe present compositions. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms.

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylated andpropoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-C₁₈ ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkylpolysaccharide surfactants, particularly for usein the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside). The inter-saccharide bonds can be, e.g., between theone position of the additional saccharide units and the 2-, 3-, 4-,and/or 6-positions on the preceding saccharide units.

Fatty acid amide surfactants suitable for use the present compositionsinclude those having the formula: R⁶CON(R⁷)₂ in which R⁶ is an alkylgroup containing from 7 to 21 carbon atoms and each R⁷ is independentlyhydrogen, C₁-C₄ alkyl, C₄ hydroxyalkyl, or —(C₂H₄O)_(x)H, where x is inthe range of from 1 to 3.

A useful class of non-ionic surfactants include the class defined asalkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)_(s)N-(EO)_(t)H, R²⁰—(PO)_(s)N-(EO)_(t)H(EO)_(t)H, andR²⁰—N(EO)_(t)H; in which R²⁰ is an alkyl, alkenyl or other aliphaticgroup, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20,preferably 2-5, and t is 1-10, preferably 2-5. Other variations on thescope of these compounds may be represented by the alternative formula:R²⁰—(PO)_(v)—N[(EO)_(w)H][(EO)_(z)H] in which R²⁰ is as defined above, vis 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and z areindependently 1-10, preferably 2-5. These compounds are representedcommercially by a line of products sold by Huntsman Chemicals asnonionic surfactants. A preferred chemical of this class includesSURFONIC™ PEA 25 Amine Alkoxylate. Preferred nonionic surfactants forthe compositions of the invention include alcohol alkoxylates, EO/POblock copolymers, alkylphenol alkoxylates, and the like.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present invention. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and detergents”(Vol. I and II by Schwartz, Perry and Berch).

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, fully capped orpartially EO/PO copolymers, alcohol alkoxylates, capped alcoholalkoxylates, mixtures thereof, or the like. Suitable alkoxylatedsurfactants for use as solvents include EO/PO block copolymers, such asthe Pluronic and reverse Pluronic surfactants; alcohol alkoxylates, suchas Dehypon LS-54 (R-(EO)5(PO)4) and Dehypon LS-36 (R-(EO)3(PO)6); andcapped alcohol alkoxylates, such as Plurafac LF221 and Tegoten EC11;mixtures thereof, or the like.

When the composition is not a cleaning composition, it can be free of anonionic surfactant.

Semi-Polar Nonionic Surfactants

The cleaning composition or detergent composition can comprise asemi-polar nonionic surfactant.

The semi-polar type of nonionic surfactants is another class of nonionicsurfactants useful in compositions disclosed herein. Generally,semi-polar nonionic surfactants are high foaming agents and foamstabilizers, which can limit their application in CIP systems. However,in some embodiments designed for high foaming composition or cleaningcomposition, semi-polar nonionic surfactants would have immediateutility. The semi-polar nonionic surfactants include, but are notlimited to, the amine oxides, phosphine oxides, sulfoxides and theiralkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkyleneor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are dodecyldimethylamine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water-solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R₁ is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 toabout 24 carbon atoms in chain length; and, R₂ and R₃ are each alkylmoieties separately selected from alkyl or hydroxyalkyl groupscontaining 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphoneoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyldecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include the watersoluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R₁ is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbonatoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxylsubstituents; and R₂ is an alkyl moiety consisting of alkyl andhydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants for the compositions of the inventioninclude dimethyl amine oxides, such as lauryl dimethyl amine oxide,myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinationsthereof, and the like. Useful water soluble amine oxide surfactants areselected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallowalkyl di-(lower alkyl) amine oxides, specific examples of which areoctyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamineoxide, undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Alternatively, the cleaning composition or detergent compositiondisclosed herein can be free of a semi-polar nonionic surfactant.

Cationic Surfactants

The cleaning composition or detergent composition can comprise acationic surfactant.

Surface active substances are classified as cationic if the charge onthe hydrotrope portion of the molecule is positive. Surfactants in whichthe hydrotrope carries no charge unless the pH is lowered close toneutrality or lower, but which are then cationic (e.g. alkyl amines),are also included in this group. In theory, cationic surfactants may besynthesized from any combination of elements containing an “onium”structure RnX+Y— and could include compounds other than nitrogen(ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium). Inpractice, the cationic surfactant field is dominated by nitrogencontaining compounds, probably because synthetic routes to nitrogenouscationics are simple and straightforward and give high yields ofproduct, which can make them less expensive.

Cationic surfactants preferably include, and more preferably refer to,compounds containing at least one long carbon chain hydrophobic groupand at least one positively charged nitrogen. The long carbon chaingroup may be attached directly to the nitrogen atom by simplesubstitution; or more preferably indirectly by a bridging functionalgroup or groups in so-called interrupted alkylamines and amido amines.Such functional groups can make the molecule more hydrophilic and/ormore water dispersible, more easily water solubilized by co-surfactantmixtures, and/or water soluble. For increased water solubility,additional primary, secondary or tertiary amino groups can beintroduced, or the amino nitrogen can be quaternized with low molecularweight alkyl groups. Further, the nitrogen can be a part of branched orstraight chain moiety of varying degrees of unsaturation or of asaturated or unsaturated heterocyclic ring. In addition, cationicsurfactants may contain complex linkages having more than one cationicnitrogen atom.

The surfactant compounds classified as amine oxides, amphoterics andzwitterions are themselves typically cationic in near neutral to acidicpH solutions and can overlap surfactant classifications.Polyoxyethylated cationic surfactants generally behave like nonionicsurfactants in alkaline solution and like cationic surfactants in acidicsolution.

The simplest cationic amines, amine salts and quaternary ammoniumcompounds can be schematically drawn thus:

in which, R represents an alkyl chain, R′, R″, and R′″ may be eitheralkyl chains or aryl groups or hydrogen and X represents an anion. Theamine salts and quaternary ammonium compounds are preferred forpractical use in this invention due to their high degree of watersolubility.

Most large volume commercial cationic surfactants can be subdivided intofour major classes and additional sub-groups known to those skilled inthe art and described in “Surfactant Encyclopedia”, Cosmetics &Toiletries, Vol. 104 (2) 86-96 (1989). The first class includesalkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourthclass includes quaternaries, such as alkylbenzyldimethylammonium salts,alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammoniumsalts, and the like. Cationic surfactants are known to have a variety ofproperties that can be beneficial in the present compositions. Thesedesirable properties can include detergency in compositions of or belowneutral pH, antimicrobial efficacy, thickening or gelling in cooperationwith other agents, and the like.

Cationic surfactants useful in the compositions disclosed herein includethose having the formula R¹ _(m)R² _(x)Y_(L)Z wherein each R¹ is anorganic group containing a straight or branched alkyl or alkenyl groupoptionally substituted with up to three phenyl or hydroxy groups andoptionally interrupted by up to four of the following structures:

or an isomer or mixture of these structures, and which contains fromabout 8 to 22 carbon atoms. The R¹ groups can additionally contain up to12 ethoxy groups and m is a number from 1 to 3. Preferably, no more thanone R₁ group in a molecule has 16 or more carbon atoms when m is 2 ormore than 12 carbon atoms when m is 3. Each R₂ is an alkyl orhydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl groupwith no more than one R² in a molecule being benzyl, and x is a numberfrom 0 to 11, preferably from 0 to 6. The remainder of any carbon atompositions on the Y group are filled by hydrogens.

Y is can be a group including, but not limited to:

or a mixture thereof. Preferably, L is 1 or 2, with the Y groups beingseparated by a moiety selected from R¹ and R² analogs (preferablyalkylene or alkenylene) having from 1 to about 22 carbon atoms and twofree carbon single bonds when L is 2. Z is a water-soluble anion, suchas a halide, sulfate, methylsulfate, hydroxide, or nitrate anion,particularly preferred being chloride, bromide, iodide, sulfate ormethyl sulfate anions, in a number to give electrical neutrality of thecationic component.

Alternatively, the cleaning composition or detergent compositiondisclosed herein can be free of a cationic surfactant.

Amphoteric Surfactants

The cleaning composition or detergent composition can comprise anamphoteric surfactant.

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be any of anionic or cationic groups described herein forother types of surfactants. A basic nitrogen and an acidic carboxylategroup are the typical functional groups employed as the basic and acidichydrophilic groups. In a few surfactants, sulfonate, sulfate,phosphonate or phosphate provide the negative charge.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphato, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989), which is herein incorporated by reference in its entirety. Thefirst class includes acyl/dialkyl ethylenediamine derivatives (e.g.2-alkyl hydroxyethyl imidazoline derivatives) and their salts. Thesecond class includes N-alkylamino acids and their salts. Someamphoteric surfactants can be envisioned as fitting into both classes.

Amphoteric surfactants can be synthesized by methods known to those ofskill in the art. For example, 2-alkyl hydroxyethyl imidazoline issynthesized by condensation and ring closure of a long chain carboxylicacid (or a derivative) with dialkyl ethylenediamine. Commercialamphoteric surfactants are derivatized by subsequent hydrolysis andring-opening of the imidazoline ring by alkylation—for example withchloroacetic acid or ethyl acetate. During alkylation, one or twocarboxy-alkyl groups react to form a tertiary amine and an ether linkagewith differing alkylating agents yielding different tertiary amines.

Long chain imidazole derivatives having application in the presentinvention generally have the general formula:

wherein R is an acyclic hydrophobic group containing from about 8 to 18carbon atoms and M is a cation to neutralize the charge of the anion,generally sodium. Commercially prominent imidazoline-derived amphotericsthat can be employed in the present compositions include for example:cocoamphopropionate, cocoamphocarboxy-propionate, cocoamphoglycinate,cocoamphocarboxy-glycinate, cocoamphopropyl-sulfonate, andcocoamphocarboxy-propionic acid. Amphocarboxylic acids can be producedfrom fatty imidazolines in which the dicarboxylic acid functionality ofthe amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

The carboxymethylated compounds (glycinates) described herein abovefrequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionicSurfactants.

Long chain N-alkylamino acids are readily prepared by reaction RNH₂, inwhich R=C₈-C₁₈ straight or branched chain alkyl, fatty amines withhalogenated carboxylic acids. Alkylation of the primary amino groups ofan amino acid leads to secondary and tertiary amines. Alkyl substituentsmay have additional amino groups that provide more than one reactivenitrogen center. Most commercial N-alkylamine acids are alkylderivatives of beta-alanine or beta-N(2-carboxyethyl) alanine. Examplesof commercial N-alkylamino acid ampholytes having application in thisinvention include alkyl beta-amino dipropionates, RN(C₂H₄COOM)₂ andRNHC₂H₄COOM. In an embodiment, R can be an acyclic hydrophobic groupcontaining from about 8 to about 18 carbon atoms, and M is a cation toneutralize the charge of the anion.

Suitable amphoteric surfactants include those derived from coconutproducts such as coconut oil or coconut fatty acid. Additional suitablecoconut derived surfactants include as part of their structure anethylenediamine moiety, an alkanolamide moiety, an amino acid moiety,e.g., glycine, or a combination thereof; and an aliphatic substituent offrom about 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can alsobe considered an alkyl amphodicarboxylic acid. These amphotericsurfactants can include chemical structures represented as:C₁₂-alkyl-C(O)—NH—CH₂—CH₂—N+(CH₂—CH₂—CO₂Na)₂—CH₂—CH₂—OH orC₁₂-alkyl-C(O)—N(H)—CH₂—CH₂—N+(CH₂—CO₂Na)₂-CH₂—CH₂—OH. Disodiumcocoampho dipropionate is one suitable amphoteric surfactant and iscommercially available under the tradename MIRANOL™ FBS from RhodiaInc., Cranbury, N.J. Another suitable coconut derived amphotericsurfactant with the chemical name disodium cocoampho diacetate is soldunder the tradename MIRATAINE™ JCHA, also from Rhodia Inc., Cranbury,N.J.

A typical listing of amphoteric classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated by reference in theirentirety.

Alternatively, the cleaning composition or detergent compositiondisclosed herein can be free of an amphoteric surfactant.

Zwitterionic Surfactants

The cleaning composition or detergent composition can comprise azwitterionic surfactant.

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionic surfactants generally contain cationic and anionic groupswhich ionize to a nearly equal degree in the isoelectric region of themolecule and which can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate.

Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein. A general formula for these compounds is:

wherein R₁ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from0 to 1 glyceryl moiety; Y is selected from the group consisting ofnitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfuratom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene orhydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Zis a radical selected from the group consisting of carboxylate,sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed aboveinclude:4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate;3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate;3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; andS[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.The alkyl groups contained in said cleaning composition surfactants canbe straight or branched and saturated or unsaturated.

The zwitterionic surfactant suitable for use in the present compositionsincludes a betaine of the general structure:

wherein R′, R″, and R′″ are linear or branched alkyl or alkyl ethergroups.

These surfactant betaines typically do not exhibit strong cationic oranionic characters at pH extremes nor do they show reduced watersolubility in their isoelectric range. Unlike “external” quaternaryammonium salts, betaines are compatible with anionics. Examples ofsuitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂-14 acylamidopropylbetaine; C₈-14acylamidohexyldiethyl betaine; 4-C₁₄-16acylmethylamidodiethylammonio-1-carboxybutane; C₁₆-18acylamidodimethylbetaine; C₁₂-16 acylamidopentanediethylbetaine; andC₁₂-16 acylmethylamidodimethylbetaine.

Sultaines useful in the present invention include those compounds havingthe formula (R(R¹)₂N+R²SO₃—, in which R is a C₆-C₁₈ hydrocarbyl group,each R¹ is typically independently C₁-C₃ alkyl, e.g., methyl, and R² isa C₁-C₆ hydrocarbyl group, e.g., a C₁-C₃ alkylene or hydroxyalkylenegroup.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated in their entirety.

Alternatively, the detergent composition or cleaning compositiondisclosed herein can be free of a zwitterionic surfactant.

Gemini Surfactants

The cleaning composition or detergent composition can comprise a Geminisurfactant.

While conventional surfactants generally have one hydrophilic group andone hydrophobic group, a Gemini surfactant has at least two hydrophobicgroups and at least two hydrophilic groups. These surfactants have thegeneral formula: A1-G-A2 and get their name because they comprise twosurfactant moieties (A1, A2) joined by a spacer (G), wherein eachsurfactant moiety (A1, A2) has a hydrophilic group and a hydrophobicgroup. Generally, the two surfactant moieties (A1, A2) are the same, butthey can be different.

The Gemini surfactants may be anionic, nonionic, cationic or amphoteric.The hydrophilic and hydrophobic groups of each surfactant moiety (A1,A2) may be any of those known to be used in conventional surfactantshaving one hydrophilic group and one hydrophobic group. For example, atypical nonionic Gemini surfactant, e.g., a bis-polyoxyethylene alkylether, would contain two polyoxyethylene alkyl ether moieties.

Each moiety would contain a hydrophilic group, e.g., polyethylene oxide,and a hydrophobic group, e.g., an alkyl chain.

Anionic and nonionic Gemini surfactants include those of the formula:

wherein R³⁰ is independently C₁ to C₂₂ alkyl, R³⁴—C(O)—, or R³⁴—B—R³⁵—,wherein R³⁴ is C₁ to C₂₂ alkyl, R³⁵ is C₁ to C₁₂ alkyl, and B is anamide group, —C(O)N(R³⁶)—, an amino group —N(R³⁶)—, a carboxyl group—C(O)—O—, a carbonyl group, or a polyether group —(EO)_(a)(PO)_(b)—,wherein EO represents ethyleneoxy radicals, PO represents propyleneoxyradicals, a and b are numbers of from 0 to 100, a is preferably fromabout 0 to about 30 and b is preferably from about 0 to 10, wherein thesum of a and b is at least one, and the EO and PO radicals can berandomly mixed or in discrete blocks, and R³⁶ is hydrogen or C₁ to C₆alkyl.

R³¹ is independently hydrogen or C₁ to C₂₂ alkyl; R³² is independently aC₁-C₁₀ alkyl, —O—, an amide group —C(O)N(R⁶)—, a polyether group—O(EO)_(a)(PO)_(b)—, —R³⁷-D-R³⁷—, or -D-R³⁷-D-, wherein R³⁷ isindependently a C₁-C₆ alkyl and D is —O—, —S—, an amide group—C(O)N(R³⁶)—, or an amino group —N(R³⁶)—, wherein R³⁶, a and b are asdefined above, and t is independently 0 or 1.

Z is independently hydrogen, —SO₃Y, —P(O)(OY)₂, —COOY, —CH₂COOY,—CH₂CH(OH)CH₂SO₃Y and when R³² is not a polyether, Z is also —OSO₃Y, and—OP(O)(OY)₂; wherein Y is hydrogen, alkali metal such as sodium andpotassium; alkaline earth metal such as magnesium and calcium; ammonium;or organic base salt such as monoethanolamine, diethanolamine,triethanolamine, triethylamine, trimethylamine, N-hydroxyethylmorpholine, and the like.

A1 or A2 is independently a straight chain or branched C₁ to C₆ alkyl,an O—R⁵—O— group or aryl; preferably phenyl; R³³ is a bond, an arylgroup such as a phenyl or diphenyl group, a C₁ to C₁₀ alkyl group,preferably a C₁ to C₄ alkyl group, most preferably methylene, —C≡C—,—O—, —S—S—, —N(R₃₆)—, —R³⁵O (EO)_(a)(PO)_(b)—, -D1-R³⁸-D1- or—R³⁸-D1-R³⁸—, wherein R³⁸ is independently a C₁-C₁₀ alkyl group, —C(O)—,—R³⁵O(EO)_(a)(PO)_(b)—, or aryl, e.g. phenyl, and D1 is independently—O—, —S—S—, —SO₂—C(O)—, a polyether group —O(EO)_(a)(PO)_(b)—, an amidegroup —C(O)N(R³⁶)—, an amino group —N(R³⁶)—, —O—R⁵—O—, or aryl whereinR³⁵, R³⁶, a and b are as defined above.

On the formulae of this disclosure, the term “alkali” includessubstituted alkali, especially the hydroxy substituted derivativesthereof and straight as well as branched chains. When Z is hydrogen, thegemini surfactants are nonionic.

Other Gemini surfactants specifically useful in the present disclosureinclude gemini anionic or nonionic surfactants of the formulae:

wherein R_(c) represents aryl, preferably phenyl. R³¹, R³³, R³⁴, and Zare as defined above. a and b are numbers of from 0 to 100, a ispreferably from about 0 to about 30 and b is preferably from about 0 to10, wherein the sum of a and b is at least one, and the EO and POradicals can be randomly mixed or in discrete blocks.

The primary hydroxyl group of these surfactants can be readilyphosphated, sulfated or carboxylated by standard techniques.

Alternatively, the detergent composition or cleaning compositiondisclosed herein can free of a Gemini surfactant.

Additional Components

The cleaning composition or detergent composition disclosed herein mayalso include one or more additional cleaning composition agents.Exemplary additional cleaning composition agents include, but are notlimited to, a threshold agent; crystal modifier; hardening agent;bleaching agent; peroxycarboxylic acid, peroxycarboxylic acidcomposition, filler; defoaming agent; anti-redeposition agent;stabilizing agent; dispersant; fragrance and dye; and thickener.

Alternatively, the cleaning composition or detergent compositiondisclosed herein can be free of one, more, or all the additionalcleaning composition agents.

Preparation of Compositions Herein

In one example, a compound of formula 1 is combined with any additionalfunctional components and allowed to interact and harden into solidform. The solidification process may last from a few minutes to aboutsix hours, depending on factors including, but not limited to: the sizeof the formed or cast composition, the ingredients of the composition,and the temperature of the composition.

The solid compositions may be formed using a batch or continuous mixingsystem. In an exemplary embodiment, a single- or twin-screw extruder isused to combine and mix one or more cleaning agents at high shear toform a homogeneous mixture. In some embodiments, the processingtemperature is at or below the melting temperature of the components.The processed mixture may be dispensed from the mixer by forming,casting or other suitable means, whereupon the composition hardens to asolid form. The structure of the matrix may be characterized accordingto its hardness, melting point, material distribution, crystalstructure, and other like properties according to known methods in theart. Generally, a solid composition processed according to the method ofthe invention is substantially homogeneous with regard to thedistribution of ingredients throughout its mass and is dimensionallystable.

In an extrusion process, the liquid and solid components are introducedinto final mixing system and are continuously mixed until the componentsform a substantially homogeneous semi-solid mixture in which thecomponents are distributed throughout its mass. The mixture is thendischarged from the mixing system into, or through, a die or othershaping means. The product is then packaged. In an exemplary embodiment,the formed composition begins to harden to a solid form in fromapproximately 1 minute to approximately 3 hours. Particularly, theformed composition begins to harden to a solid form from approximately 1minute to approximately 2 hours. More particularly, the formedcomposition begins to harden to a solid form from approximately 1 minuteto approximately 20 minutes.

In a casting process, the liquid and solid components are introducedinto the final mixing system and are continuously mixed until thecomponents form a substantially homogeneous liquid mixture in which thecomponents are distributed throughout its mass. For example, thecomponents can be mixed in the mixing system for at least approximately60 seconds. Once the mixing is complete, the product is transferred to apackaging container where solidification takes place. In an exemplaryembodiment, the cast composition begins to harden to a solid form infrom approximately 1 minute to approximately 3 hours. Particularly, thecast composition begins to harden to a solid form in from approximately1 minute to approximately 2 hours. More particularly, the castcomposition begins to harden to a solid form approximately 1 minute toapproximately 20 minutes.

By the term “solid”, it is meant that the hardened composition will notflow and will substantially retain its shape under moderate stress orpressure or mere gravity. The degree of hardness of the solid castcomposition may range from that of a fused solid product which isrelatively dense and hard, for example, like concrete, to a consistencycharacterized as being a hardened paste. In addition, the term “solid”refers to the state of the composition under the expected conditions ofstorage and use of the solid composition. In general, it is expectedthat the composition will remain in solid form when exposed totemperatures of up to approximately 100° F. and particularly up toapproximately 120° F.

The resulting solid composition may take forms including, but notlimited to: a cast solid product; an extruded, pressed, molded or formedsolid pellet, block, tablet, powder, granule, flake; or the formed solidcan thereafter be ground or formed into a powder, granule, or flake. Forexample, extruded pellet materials formed by the solidification matrixcan have a weight of about 50 grams to about 250 grams, extruded solidsformed by the composition can have a weight greater than or equal toabout 100 grams, and solid block cleaning compositions formed by thecomposition can have a mass of about 1 to about 10 kilograms. The solidcompositions provide for a stabilized source of functional materials. Insome embodiments, the solid composition may be dissolved, for example,in an aqueous or other medium, to create a concentrated and/or usecomposition. The solution may be directed to a storage reservoir forlater use and/or dilution, or may be applied directly to a point of use.

The solid composition can be provided in the form of a unit dose. A unitdose refers to a solid composition unit sized so that the entire unit isused during a single washing cycle. When the solid composition isprovided as a unit dose, it is typically provided as a cast solid, anextruded pellet, or a tablet having a size of approximately 1 gram toapproximately 50 grams.

The solid composition can also be provided in the form of a multiple-usesolid, such as a block or a plurality of pellets, and can be repeatedlyused to generate aqueous compositions for multiple washing cycles. Forexample, the solid composition can be provided as a cast solid, anextruded block, or a tablet having a mass of about 5 grams to about 10kilograms, from about 1 kilogram to about 10 kilograms, or from about 5kilograms to about 8 kilograms. Alternatively, a multiple-use form ofthe solid composition can have a mass of about 5 grams to about 1kilogram or about 5 grams to about 500 grams.

Although the composition is discussed as being formed into a solidproduct, the composition may also be provided in the form of a paste orliquid. When the concentrate is provided in the form of a paste, enoughwater is added to the composition such that complete solidification ofthe composition is precluded. In addition, dispersants and othercomponents may be incorporated into the composition in order to maintaina desired distribution of components.

When used in the methods described herein below, the cleaningcompositions or detergent compositions may be ready to use solutions orconcentrate compositions which may be added to an aqueous system or maybe diluted to form use compositions. In general, a concentrate refers toa composition that is intended to be added to or diluted with water, andthe composition that contacts articles to be washed can be referred toas the use composition.

A use composition may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a usecomposition having desired detersive properties. The water that is usedto dilute the concentrate to form the use composition can be referred toas water of dilution, or a diluent, and can vary from one location toanother. The use composition can also include additional functionalingredients at a level suitable for cleaning, rinsing, or the like.

The concentrate compositions may essentially include only a compound orcompounds of formula 1, and additional components and/or functionalmaterials may be added as separate ingredients prior to the point of useor at the point of use. Alternatively, the concentrate compositions mayinclude a compound or compounds of formula 1 as well as additionalcomponents such as, but not limited to, at least one alkali metalhydroxide.

The typical dilution factor for the cleaning composition or detergentcomposition is from approximately 1 to approximately 10,000 but willdepend on factors including water hardness, the amount of soil to beremoved and the like. For example, the concentrate is diluted at a ratioof about 1:10 to about 1:1000 concentrate to water. Particularly, theconcentrate is diluted at a ratio of about 1:100 to about 1:5000concentrate to water. More particularly, the concentrate is diluted at aratio of about 1:250 to about 1:2000 concentrate to water.

For the purpose of illustration, representative non-limiting cleaning ordetergent compositions comprising the compound of Formula 1, 2 or 3 thatare useful for various applications are provided herein.

Hard Surface Dishwashing/ Cleaner/ Warewashing Manual Pot andClean-in-Place Degreaser Detergent Laundry Detergent Pan PresoakFormulation pH ≥ 2 pH ≥ 5 pH ≥ 5 pH ≥ 5 pH ≥ 1 Compound of Compound ofCompound of Compound of Compound of Formula 1, 2 or 3 Formula 1, 2 or 3Formula 1, 2 or 3 Formula 1, 2 or 3 Formula 1, 2 or 3 SurfactantAlkalinity Source Alkalinity Source Alkalinity Alkalinity SourceAlkalinity Source Surfactant Surfactant Source OR Organic or Waterconditioning Water conditioning Surfactant Organic or Inorganic Acidagents agents Water Inorganic Acid Water conditioning Enzyme Enzymeconditioning Surfactant agents Oxidizer Oxidizer agents Water SolventWater Water Enzyme conditioning Water Adjuvant Optical Brightener Wateragents Adjuvant ingredients Adjuvant ingredients Adjuvant Enzymeingredients ingredients Water Adjuvant ingredients

Methods of cleaning an article are also provided. The methods comprisecontacting the article with a detergent composition comprising acompound of Formula 1, 2, or 3 as described herein. As described above,the detergent composition can further comprise a building agent. Thebuilding agent can comprise an enzyme, an oxidizing agent, a condensedphosphate, an alkali metal carbonate, an alkali metal silicate, analkali metal metasilicate, a phosphonate, an amino carboxylic acid, acarboxylic acid polymer, or a combination thereof.

The article can be contacted with from about 50 to about 6,000 ppm ofthe cleaning composition based on the total volume of the fluid incontact with the article.

The article can be contacted with from about 10 to about 3,000 ppm ofthe compound of Formula 1, 2, or 3 based on the total volume of thefluid in contact with the article.

The article can comprise a metal surface, a glass surface, a fabric, aware, a polycarbonate surface, a polysulfone surface, a melaminesurface, a ceramic surface, a porcelain surface, or a combinationthereof. Preferably, the article is a fabric. More preferably, thearticle is a ware.

Also provided are methods for cleaning a membrane. The methods comprisecontacting the membrane with a cleaning solution comprising any compoundof Formula 1, 2, or 3 as described herein.

The membrane may be contacted with from about 10 to about 5,000 ppm ofthe compound of Formula 1, 2, or 3, based on the total weight of thefluid contacting the membrane.

In the methods disclosed herein, the membrane can be a membrane used ina dairy process. For example, the membrane can be a microfiltrationmembrane, an ultrafiltration membrane, a nanofiltration membrane, areverse osmosis membrane or a combination thereof.

Definitions

As used herein, the term “substantially free”, “free” or “free of”refers to compositions completely lacking the component or having such asmall amount of the component that the component does not affect theperformance of the composition. The component may be present as animpurity or as a contaminant and shall be less than 0.5 wt. %. Forexample, the amount of the component can less than 0.1 wt. % or, in somecases, the amount of component can be less than 0.01 wt. %.

The term “weight percent”, “wt. %”, “percent by weight”, “% by weight”,and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent”, “%”, and the like are intended to be synonymous with“weight percent”, “wt. %”, etc.

As used herein, the term “polymer” means a water-soluble orwater-dispersible polymer. The term “polymer” encompasses and includeshomopolymers, copolymers, terpolymers and polymers with more than threemonomers, crosslinked or partially crosslinked polymers, andcombinations or blends of these.

As used herein, the term “polymer solution” or “polymer dispersion”means a polymer composition substantially dispersed or dissolved inwater, a water source, or a water-based solution. Water-based solutionsinclude one or more dissolved salts, buffers, acids, bases, surfactants,or other dissolved, dispersed, or emulsified compounds, materials,components, or combinations thereof.

As used herein, “inverse emulsion polymer” and “inverse latex polymer”mean a water-in-oil polymer emulsion comprising a water-soluble polymer(which could be cationic, anionic, nonionic, amphoteric polymer, orzwitterionic) in the aqueous phase, a hydrocarbon oil for the oil phaseand a water-in-oil emulsifying agent. Inverse emulsion polymers arehydrocarbon continuous with the water-soluble polymers dispersed withinthe hydrocarbon matrix. The inverse emulsion polymers are then“inverted” or activated for use by releasing the polymer from theparticles using shear, dilution, and generally another surfactant. SeeU.S. Pat. No. 3,734,873, incorporated herein by reference.

As used herein, the term “water source” means a source of watercomprising, consisting essentially of, or consisting of fresh water,deionized water, distilled water, produced water, municipal water, wastewater such as runoff water or municipal waste water, treated orpartially treated waste water, well water, brackish water, “gray water”,sea water, or a combination of two or more such water sources asdetermined by context. A water source can include one or more salts,ions, buffers, acids, bases, surfactants, or other dissolved, dispersed,or emulsified compounds, materials, components, or combinations thereof.

As used herein, the terms “water-in-oil emulsion” mean a discontinuousinternal water phase within a continuous oil phase, wherein the waterphase includes at least one monomer or polymer. In general and asdetermined by context, these terms denote an emulsion prior to additionof inversion surfactants.

As used herein, the term “oil” or “hydrocarbon solvent” as applied to anoil phase of a water-in-oil emulsion, means any compound or blendthereof that is less than 0.1 wt % soluble in water at 25° C., issubstantially chemically inert within a water-in-oil emulsion asdescribed herein, and is a liquid over at least the range of 20° C. to100° C.

As used herein, the term “water phase” means a water source having atleast a monomer or polymer dispersed or dissolved therein, furtherwherein the dispersion or solution is a discontinuous phase within awater-in-oil emulsion.

Unless otherwise indicated, an alkyl group as described herein alone oras part of another group is an optionally substituted linear saturatedmonovalent hydrocarbon substituent containing from one to sixty carbonatoms and preferably one to thirty carbon atoms in the main chain oreight to thirty carbon atoms in the main chain, or an optionallysubstituted branched saturated monovalent hydrocarbon substituentcontaining three to sixty carbon atoms, and preferably eight to thirtycarbon atoms in the main chain. Examples of unsubstituted alkyl groupsinclude methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, and the like.

The terms “aryl” or “ar” as used herein alone or as part of anothergroup (e.g., arylalkyl) denote optionally substituted homocyclicaromatic groups, preferably monocyclic or bicyclic groups containingform 6 to 12 carbon atoms in the ring portion, such as phenyl, biphenyl,naphthyl, substituted phenyl, substituted biphenyl, or substitutednaphthyl. Phenyl and substituted phenyl are the more preferred arylgroups. The term “aryl” also includes heteroaryl functional groups.

“Arylalkyl” means an aryl group attached to the parent molecule throughan alkylene group. The number of carbon atoms in the aryl group and thealkylene group is selected such that there is a total of about 6 toabout 18 carbon atoms in the arylalkyl group. A preferred arylalkylgroup is benzyl.

The term “substituted,” as in “substituted aryl,” “substituted alkyl,”and the like, means that in the group in question (i.e., the alkyl,aryl, or other group that follows the term), at least one hydrogen atombound to a carbon atom is replaced with one or more substituent groupssuch as hydroxy (—OH), alkylthio, amido (—CON(R_(A))(R_(B)), whereinR_(A) and R_(B) are independently hydrogen, alkyl, or aryl), amino(—N(R_(A))(R_(B)), wherein R_(A) and R_(B) are independently hydrogen,alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro(—NO₂), an ether (—OR_(A) wherein R_(A) is alkyl or aryl), an ester(—OC(O)R_(A) wherein R_(A) is alkyl or aryl), keto (—C(O)R_(A) whereinR_(A) is alkyl or aryl), heterocyclo, and the like. When the term“substituted” introduces a list of possible substituted groups, it isintended that the term apply to every member of that group. That is, thephrase “optionally substituted alkyl or aryl” is to be interpreted as“optionally substituted alkyl or optionally substituted aryl.”

The term “heterocyclo,” “heterocycle,” or “heterocyclyl,” as usedherein, refers to a monocyclic, bicyclic, or tricyclic group containing1 to 4 heteroatoms selected from N, O, S(O)n, P(O)n, PRz, NH or NRz,wherein Rz is a suitable substituent. Heterocyclic groups optionallycontain one or two double bonds. Heterocyclic groups include, but arenot limited to, azetidinyl, tetrahydrofuranyl, imidazolidinyl,pyrrolidinyl, piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl,pyrazolidinyl, thiomorpholinyl, tetrahydrothiazinyl,tetrahydro-thiadiazinyl, morpholinyl, oxetanyl, tetrahydrodiazinyl,oxazinyl, oxathiazinyl, indolinyl, isoindolinyl, quinuclidinyl,chromanyl, isochromanyl, and benzoxazinyl. Examples of monocyclicsaturated or partially saturated ring systems are tetrahydrofuran-2 yl,tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2 yl,imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2 yl, pyrrolidin-3-yl,piperidin-1-yl, piperidin-2 yl, piperidin-3-yl, piperazin-1-yl,piperazin-2 yl, piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine,1,3-thiazolidin-3-yl, 1,2 pyrazolidin-2 yl, 1,3-pyrazolidin-1-yl,thiomorpholin-yl, 1,2 tetrahydrothiazin-2 yl,1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-yl, morpholin-yl, 1,2tetrahydrodiazin-2 yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-2 yl, and1,2,5 oxathiazin-4-yl. Heterocyclic groups can be unsubstituted orsubstituted by one or more suitable substituents, preferably 1 to 3suitable substituents, as defined above.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

EXAMPLES

The following non-limiting examples are provided to further illustratethe present invention.

Example A: Synthesis of Novel Surfactant Compositions

The overall synthesis of the surfactants described herein is achieved intwo steps (Scheme 1). Acceptor molecule (C) is first prepared by ringopening reaction of an alkyl-epoxide (II) with an aromatic amine oralcohol compound (A). The second step involves oxyalkylation of theacceptor molecule (C) with alkylene oxide (D) to afford a series ofsurfactants (E).

wherein X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, m, and n are defined above.

Examples 1 and 2 disclose the specific synthesis of a series ofethoxylated 1-((2-ethylhexyl)oxy-3-phenoxypropan-2-ol via the followingtwo step process (Scheme 2):

Example 1A: Synthesis of 1-((2-ethylhexyl)oxy)-3-phenoxypropan-2-ol

TABLE 1 Reagent MW(g/mol) Mass(g) n(mole) Phenol 94.11 100 1.062-Ethylhexyl glycidyl 186.29 200 1.06 ether KOH Pallets 56.11 1 0.02

Phenol (100 g, 1.06 mole) and potassium hydroxide (1 g, 0.02 mole) wereadded to a 500 mL three necked round-bottom flask equipped withtemperature probe, condenser, nitrogen inlet and magnetic stir bar andthe temperature of the reaction increased to 50° C. 2-Ethylhexylglycidalether (200 g, 1.06 moles) was then added to the molten phenol undernitrogen blanket. The temperature of the reaction was further increasedto 130° C. and stirred for 4 hours or until completion of reaction. Theprogress of the reaction was monitored by GC-MS (FIG. 1). The structureof the resulting compound was confirmed by NMR (FIG. 2) and massspectrometry (+ESI-MS): calc. [M+H]+ 281.21, found 281.2109.

Example 1B: Addition of Ethylene Oxide to the1-((2-ethylhexyl)oxy)-3-phenoxypropan-2-ol

After catalyzing and dehydrating, 505.93 g of1-((2-ethylhexyl)oxy-3-phenoxypropan-2-ol was charged to a 2-liter Parrreactor and heated to 125° C. under 10 psi of nitrogen at a stirrerspeed of 300 rpm. The ethoxylation reaction was initiated when theacceptor material reached 125° C. The ethylene oxide was charged instep-wise fashion to slowly increase the working pressure range of 55-65psi during the oxide feed. A slight exotherm was observed. Once thetarget amount of ethylene oxide, 476.5 g (6 mol), was charged to thereactor, the oxide feed was discontinued and the reaction was allowed toproceed for 6 hours at 125° C. The material was then cooled and sampledfor testing. Preparation of intermediates with increasing levels ofethylene oxide (6-13 mol EO) was completed through addition of thedesired amounts of EO.

Example 2A: Synthesis of3,3′-((4-hydroxyphenyl)azanediyl)bis(1-((2-ethylhexyl)oxy)propan-2-ol)

TABLE 1 Reagent MW(g/mol) Mass(g) n(moles) 4-Aminophenol 109.13 1761.612 2-ethylhexylglycidyl 186.29 600 3.22 ether

To a 1 L three necked round-bottom flask equipped with temperatureprobe, nitrogen inlet, condenser and magnetic stir bar was added2-ethylhexylglycidal ether (600 g, 3.22 moles). 4-Aminophenol (176 g,1.612 mole) was then added to the well-stirred reaction mixture. Theresulting suspension was heated to 120° C. under a nitrogen blanket andstirred for 3 hours or until the reaction was completed. As the reactionproceeded to completion, the suspension turned into a homogenousdark-amber product. The resulting product was characterized by NMR andESI-MS.

Example 2B: Addition of Ethylene Oxide to the3,3′-((4-hydroxyphenyl)azanediyl)bis(1-((2-ethylhexyl)oxy)propan-2-ol)

After catalyzing and dehydrating, 481.72 g of3,3′-((4-hydroxyphenyl)azanediyl)bis(1-((2-ethylhexyl)oxy)propan-2-ol)was charged to a 2-liter Parr reactor and heated to 125° C. under 10 psiof nitrogen at a stirrer speed of 300 rpm. The ethoxylation reaction wasinitiated when the acceptor material reached 125° C. The ethylene oxidewas charged in step-wise fashion to slowly increase the working pressurerange of 55-65 psi during the oxide feed. A slight exotherm wasobserved. Once the target amount of ethylene oxide, 440.5 g (10 mol),was charged to the reactor, the oxide feed was discontinued and thereaction was allowed to proceed for 6 hours at 125° C. The material wasthen cooled and sampled for testing. Preparation of intermediates withincreasing levels of ethylene oxide (10-24 mol O-EO) was completedthrough addition of the desired amounts of EO.

Example B: Materials and Methods for Examples 3 to 6

Activating Surfactants:

Surfactants listed in table below were used for evaluation testing.

TABLE 2 Activators and Surfactants ID used in Description the examplesType Dow Tergitol NP-9.5 Activator #1 Nonylphenol ethoxylate SasolAlfonic 1412-7 Activator #2 Alcohol ethoxylate Huntsman Surfonic TDA-9Activator #3 Alcohol ethoxylate Huntsman Surfonic TDA-12 Activator #4Alcohol ethoxylate NP-12 (NPE with 12 moles Activator #5 Nonylphenolethoxylate of EO) 1-((2-ethylhexyl)oxy)- nEO, where n Surfactants(Prepared as 3-phenoxypropan-2-ol indicates moles in Examples 1A and 1B)ethoxylate of EO unitsPreparation of Polymer Blends:

The polymer blends containing inverting surfactants (at theconcentrations indicated in the examples) were prepared directly in 4oz. jars. The inverting surfactant was added drop-wise to theun-activated latex while mixing at 800 rpm with a small cage stirrer.Following addition, the resulting mixture was stirred for one hour andthen allowed to equilibrate for at least two additional hours.

Preparation of Synthetic Sea Water (SSW)

The 3.5% synthetic seawater was prepared by blending the components ofTable 3. SSW was filtered through a WHATMAN 1 filter by suctionfiltration to remove any particulates.

TABLE 3 Ingredients of 3.5% SSW Reagent Amount (g) Sodium chloride(NaCl) 73.95 Calcium chloride CaCl₂•2H₂O 4.71 Magnesium chloride(MgCl₂•6H₂O) 341.7 Sodium bicarbonate (NaHCO₃) 0.03 Sodium sulfate(Na₂SO₄) 13.14 Deionized water 2873.97 Total 3000Preparation of High Total Dissolved Solids (TDS) Brine (12.5%)

The 12.5% TDS brine was prepared by blending the components of Table 4.Brine was filtered through a WHATMAN 1 filter by suction filtration toremove any particulates.

TABLE 4 Ingredients of 12.5% TDS brine Reagent Amount (g) Sodiumchloride (NaCl) 91.83 Calcium chloride CaCl₂•2H₂O 21.60 Magnesiumchloride (MgCl₂•6H₂O) 7.71 Potassium chloride (KCl) 0.908 Strontiumchloride SrCl₂ 6H₂O 1.179 Deionized water 876.77 Total 1000Evaluation Method: Inversion Torque Monitor

The rate of inversion, or rate of viscosity build, is an importantdeterminant of activity for emulsion inverse polymers. Fieldapplications generally require that inversion occurs rapidly. In thelaboratory, the rate and extension of inversion of polymer blendscontaining different surfactants is determined by analytical toolreferred to as an “inversion torque monitor (ITM).” The inversionefficacy of surfactants was compared to some commonly used inverters (byNalco in polymer formulations) using ITM.

The ITM consisted of a DC stir motor, a controller that can report thetorque (DC voltage) required to maintain a constant stir speed, and acomputer to record the torque reading as a function of time. This methodinvolves injecting polymer blends into a larger volume of solvent whilerecording the force required to turn a large cage stirrer at a specifiedRPM in the inverting solution. Torque readings were collected everysecond and data worked-up in Microsoft Excel using a 20-period movingaverage.

Conditions: Torque monitor tests were conducted at the 500 g scale in a1000-mL beaker with an HS-1 “Jiffy Mixer” cage paddle connected to themotor in different waters (tap water from the City of Naperville, Ill.;synthetic sea water; high TDS brine) at different temperatures (4° C.,22° C., 60° C.) at the concentrations indicated in the examples unlessotherwise noted. All tests were run at a stir speed of 400 rpm. Thewater temperature was controlled with a circulating heating/cooling baththrough the jacketed beaker. When the water temperature reached thetarget test temperature, the latex was shot into the stirred water froma disposable syringe and the torque was continuously recorded for 30minutes and data was worked-up in Microsoft Excel using a 20-periodmoving average. The analysis was run for 30 minutes to confirm thetorque remained stable.

Data: Four pieces of data are determined by Torque measurements: timedifferential between when the latex was injected and the torque began toincrease (“Induction Period”), time until the maximum torque was reached(“Hydration Period”), the value of the maximum torque, and the percentinversion at 2 minutes and 5 minutes (estimated from 2 and 5 minutetorque readings compared to the final torque readings).

Plots of torque versus time provide a way to evaluate the speed at whichinversion takes place, and also the extent of inversion. The slope ofthe torque versus time curve in the early portion of the experiment is agood indicator of how rapidly inversion occurs. The torque typicallylevels off to form a plateau region. Higher levels of torque in theplateau region generally indicate a higher emulsion viscosity.

Relative performance of different surfactants for inversion was assessedby the induction time, hydration time, and torque values in the plateauregion. Shorter hydration period as well as higher level of torque inthe plateau region indicates better performance of inverting surfactant.

Example 3: Evaluation of Surfactants for Inversion of Anionic InversionEmulsion (Mobility Control, EOR) Polymers in Synthetic Sea Water atDifferent Temperatures

Un-activated 7:3 acrylamide/acrylic acid emulsion co-polymer (emulsionpolymer 1) without activating surfactant was used in this example.

Example 3A: Performance Evaluation in Synthetic Sea Water at 22° C.

Blend preparation and activator concentration: Polymer 1 blends with2.0% activator were prepared by blending activator into the emulsionwhile stirring at room temperature.

Conditions: The synthetic seawater (SSW) in the torque monitor apparatuscontained 3.5% salts with an equivalent hardness of 6600 ppm of CaCO3and was maintained at 25° C. An amount of the invertible latex injectedinto the stirred water in the torque monitor apparatus yielded a dilutelatex having 1% polymer.

Results: FIG. 3 depicts the inversion torque profiles at 22° C. forpolymer 1 (1% invert in SSW) blends with 2.0% activating surfactants.Table 5 shows induction period, hydration time and maximum torque values(in the plateau region) determined from torque experiments for polymer 1blends.

Discussion: The data of Table 5 and FIG. 3 demonstrate that, at 22° C.,the blends of polymer 1 comprising 2 wt % of a surfactant exhibit fasteror comparable inversion rates (as indicated by hydration time) andgreater or comparable extent of inversion (as indicated by maximumtorque value) than polymer 1 blends comprising 2 wt % of an alcoholethoxylate or a NPE ethoxylate surfactant. Alcohol ethoxylates(activator 2 and activator 3) performed poorly as maximum torque inrange of 100-120 cm-g was achieved at 1800 seconds for the blendscomprising them. Activator 13EO was the best performing surfactant amongall tested surfactants.

In all cases, at the end of the test, the dilute latex solutions wereobserved to be fully dispersed, that is, no residual clumps oraggregates of material were observed.

TABLE 5 Inversion torque measurements for Polymer 1 blends comprising 2%activators Induction period Hydration time Max Torque Surfactant (sec)(sec) (g · cm) 10EO 30 1080  525 11EO 30 360 525 12EO 30 360 520 13EO 30210 520 Activator 1 30 780 450 Activator 2 360 — 100 Activator 3 390 —120 Activator 4 30 300 500

Example 3B: Performance Evaluation in Synthetic Sea Water at 4° C.

Blend preparation and activator concentration: Polymer 1 blends with3.0% activator were prepared by blending activator into the emulsionwhile stirring at room temperature.

Conditions: The synthetic seawater (SSW) in the torque monitor apparatuscontained 3.5% salts with an equivalent hardness of 6600 ppm of CaCO3and was maintained at 4° C. An amount of the invertible latex injectedinto the stirred water in the torque monitor apparatus yielded a dilutelatex having 1% polymer.

Results: FIG. 4 depicts the inversion torque profiles at 4° C. forpolymer 1 (1% invert in SSW) blends with 3.0% activating surfactants.Table 6 shows induction period, hydration time and maximum torque values(in the plateau region) determined from torque experiments for polymer 1blends with 3.0% activating surfactants.

Discussion: The data of Table 6 and FIG. 4 demonstrate that, at 4° C.,the blends of polymer 1 comprising 3 wt % of a surfactant exhibit fasteror comparable inversion rates (as indicated by hydration time) andgreater or comparable extent of inversion (as indicated by maximumtorque value) than polymer 1 blends comprising 2 wt % of an alcoholethoxylate or a NPE ethoxylate surfactant. A maximum torque in range of500-510 cm-g was achieved within 600 seconds for all the blends.

In all cases, at the end of the test, the dilute latex solutions wereobserved to be fully dispersed, that is, no residual clumps oraggregates of material were observed.

TABLE 6 Inversion Torque Measurements for Polymer 1 blends comprising 3%Activators at 4° C. Induction period Hydration time Max TorqueSurfactant (sec) (sec) (g · cm) 10EO 45 240 530 11EO 45 210 510 12EO 45210 510 13EO 30 600 510 Activator 1 30 240 500 Activator 2 45 240 510Activator 4 30 420 500

Example 3C: Performance Evaluation in Synthetic Sea Water at 60° C.

Blend preparation and activator concentration: Polymer 1 blends with3.0% activator were prepared by blending activator into the emulsionwhile stirring at room temperature.

Conditions: The synthetic seawater (SSW) in the torque monitor apparatuscontained 3.5% salts with an equivalent hardness of 6600 ppm of CaCO3and was maintained at 60° C. An amount of the invertible latex injectedinto the stirred water in the torque monitor apparatus yielded a dilutelatex having 1% polymer.

Results: FIG. 5 depicts the inversion torque profiles at 60° C. forpolymer 1 (1% invert in SSW) blends with 3.0% activating surfactants.Table 7 shows induction period, hydration time and maximum torque values(in the plateau region) determined from torque experiments for eachpolymer 1 blend.

Discussion: The data of Table 7 and FIG. 5 demonstrate that, at 60° C.,the blends of polymer 1 comprising 3 wt % of a surfactant exhibit fasterinversion rates (as indicated by hydration time) and greater extent ofinversion (as indicated by maximum torque value) than polymer 1 blendscomprising 3 wt % of an alcohol ethoxylate or a NPE ethoxylatesurfactant. Alcohol ethoxylate (activator 2) performed poorly as amaximum torque of about 180 cm-g was achieved at 1800 seconds for theblend comprising it. Activator 13EO was the best performing surfactantamong all tested surfactants.

In all cases except for polymer blend 1 comprising 3% activator 2, atthe end of the test, the dilute latex solutions were observed to befully dispersed, that is, no residual clumps or aggregates of materialwere observed.

TABLE 7 Inversion Torque measurements for Polymer 1 blends comprising 3%activators at 60° C. Induction period Hydration time Max TorqueSurfactant (sec) (sec) (g · cm) 11EO 90 1020 250 12EO 30 180 310 13EO 15120 330 Activator 1 120 1500 300 Activator 2 690 120 180 Activator 4 15— 320

Example 4: Evaluation of Surfactants for Inversion of Anionic InverseEmulsion (Friction Reducing) Polymers in High TDS Brines

Un-activated 8:2 acrylamide/acrylic acid emulsion co-polymer (emulsionPolymer 2) without activating surfactant was used in this example.

Example 4A: Performance Evaluation in 4% KCl Solution at 22° C.

Blend preparation and activator concentration: Polymer 2 blends with3.0% activator were prepared by blending activator into the emulsionwhile stirring at room temperature.

Conditions: The water in the torque monitor apparatus contained 4%potassium chloride salts and was maintained at 25° C. An amount of theinvertible latex injected into the stirred water in the torque monitorapparatus yielded a dilute latex having 1% polymer.

Results: FIG. 6 depicts the inversion torque profiles at 22° C. forPolymer 2 (1% invert in SSW) blends with 3.0% activating surfactants.Table 8 shows induction period, hydration time and maximum torque values(in the plateau region) determined from torque experiments for polymer 2blends.

Discussion: The data of Table 8 and FIG. 6 demonstrate that, at 22° C.,the blends of Polymer 2 comprising 3 wt % of a surfactant of currentinvention exhibit faster or comparable inversion rates (as indicated byhydration time) and greater or comparable extent of inversion (asindicated by maximum torque value) than Polymer 1 blends comprising 3wt. % of an alcohol ethoxylate or a NPE ethoxylate surfactant. A maximumtorque in range of 600-620 cm-g was achieved within 150 seconds for allthe blends.

In all cases, at the end of the test, the dilute latex solutions wereobserved to be fully dispersed, that is, no residual clumps oraggregates of material were observed.

TABLE 8 Inversion torque measurements for Polymer 2 blends comprising 3%activators in 4% KCl solution Induction period Hydration time Max TorqueSurfactant (sec) (sec) (g/cm) 9EO 15 300 640 10EO 10 120 600 11EO 15 150600 12EO 15 150 610 Activator 1 15 150 630 Activator 2 30 300 620Activator 4 15 180 600

Example 4B: Performance Evaluation in High Stress Conditions Such as TDS(12.5%) Brine

Blend preparation and activator concentration: Polymer 2 blends with3.0% activator were prepared by blending activator into the emulsionwhile stirring at room temperature.

Conditions: The water in the torque monitor apparatus contained 12.5%salts and was maintained at 22° C. An amount of the invertible latexinjected into the stirred water in the torque monitor apparatus yieldeda dilute latex having 1% polymer.

Results: FIG. 7 depicts the inversion torque profiles at 22° C. forpolymer 2 (1% invert in SSW) blends with 3.0% activating surfactants.Table 9 shows induction period, hydration time and maximum torque values(in the plateau region) determined from torque experiments for polymer 2blends.

Discussion: The data of Table 9 and FIG. 7 demonstrate that, at 22° C.,the blends of polymer 2 comprising 3 wt. % of a surfactant exhibitfaster inversion rates (as indicated by hydration time) and greaterextent of inversion (as indicated by maximum torque value) than polymer2 blends comprising 3 wt. % of an alcohol ethoxylate or a NPE ethoxylatesurfactant under high stress conditions such as high TDS (12.5%) brine.Alcohol ethoxylates (activator 2 and activator 3) performed poorly as amaximum torque in range of 125-900 cm-g was achieved at 1800 seconds forthe blends comprising them. Activator 13EO was the best performingsurfactant among all tested surfactants. This example demonstrates thesuperior efficacy of inversion of anionic emulsion polymer 2 compared toother surfactants, especially under high stress conditions such as highTDS.

In all cases except for polymer blend 2 comprising 3% activator 4, atthe end of the test, the dilute latex solutions were observed to befully dispersed, that is, no residual clumps or aggregates of materialwere observed.

TABLE 9 Inversion torque measurements for Polymer 2 blends comprising 3%activators in high TDS brine. Induction period Hydration time Max TorqueSurfactant (sec) (sec) (g · cm) 11EO 60 600 450 12EO 30 540 500 13EO 30180 510 Activator 1 30 720 125 Activator 2 300 — 380 Activator 4 300 —190

Example 5: Evaluation of Surfactants for Inversion of Cationic InverseEmulsion Polymers in Tap Water Example 5A: Performance Evaluation forInversion of 50 Mol % Cationic Polymer in Tap Water from the City ofNaperville, Ill., at Room Temperature

Latex: Un-activated 1:1 Acrylamide/DMAEA⋅MCQ emulsion co-polymer(emulsion polymer 3) without activating surfactant was used in thisexample.

Blend preparation and activator concentration: Polymer 3 blends with1.8% activator were prepared by blending activator into the emulsionwhile stirring at room temperature.

Conditions: The tap water from the City of Naperville, Ill. was used fortorque monitor experiments and was maintained at 22° C. An amount of theinvertible latex injected into the stirred water in the torque monitorapparatus yielded a dilute latex having 0.5% polymer.

Results: FIG. 8 depicts the inversion torque profiles at 22° C. forpolymer 3 (0.5% invert in SSW) blends with 1.8% activating surfactants.Table 10 shows induction period, hydration time and maximum torquevalues (in the plateau region) determined from torque experiments forpolymer 3 blends.

Discussion: The data of Table 10 and FIG. 8 demonstrate that, at 22° C.,the blends of polymer 3 comprising 1.8 wt % of surfactant exhibit fasteror comparable inversion rates (as indicated by hydration time) andgreater or comparable extent of inversion (as indicated by maximumtorque value) than polymer 3 blends comprising 1.8 wt % of an alcoholethoxylate or a NPE ethoxylate surfactant in tap water. A maximum torquein range of 450-500 cm-g was achieved within 180 seconds for all theblends except for a polymer blend comprising activator 3. Alcoholethoxylate (activator 3) performed poorly as a maximum torque in rangeof 250 cm-g was achieved at 1800 second for the blend comprising it.Activators 11EO and 12EO were the best performers among all testedsurfactants.

In all cases, at the end of the test, the dilute latex solutions wereobserved to be fully dispersed, that is, no residual clumps oraggregates of material were observed.

TABLE 10 Inversion torque measurements for Polymer 3 blends comprising1.8% activators Induction period Hydration time Max Torque Surfactant(sec) (sec) (g · cm) 10EO 10 180 470 11EO 5 120 490 12EO 5 120 500 13EO5 180 460 Activator 1 5 180 450 Activator 3 30 — 250

Example 5B: Performance Evaluation for Inversion of 30 Mol % CationicPolymer in Tap Water from the City of Naperville, Ill. at RoomTemperature

Latex: Hard-to-invert un-activated 7:3 acrylamide/DADMAC(polydiallyldimethylammonium chloride) emulsion co-polymer (emulsionpolymer 4) without an activating surfactant was used in this example.

Blend preparation and activator concentration: Polymer 4 blends with 2%activator were prepared by blending activator into the emulsion whilestirring at room temperature.

Conditions: The tap water from the City of Naperville, Ill. was used fortorque monitor experiments and was maintained at 25° C. An amount of theinvertible latex injected into the stirred water in the torque monitorapparatus yielded a dilute latex having 1% polymer.

Results: FIG. 9 depicts the inversion torque profiles at 22° C. forpolymer 4 (1% invert in SSW) blends with 2% activating surfactants.Table 11 shows induction period, hydration time and maximum torquevalues (in the plateau region) determined from torque experiments forpolymer 4 blends.

Discussion: The data of Table 11 and FIG. 9 demonstrate that, at 22° C.,the blends of polymer 4 comprising 2 wt % of a surfactant havecomparable inversion rates (as indicated by inversion % at 2 minutes and5 minutes) and comparable extent of inversion (as indicated by maximumtorque value) than polymer 4 blends comprising 2 wt % of an alcoholethoxylate or a NPE ethoxylate surfactant in tap water. A maximum torquein range of 120-130 cm-g was achieved at 1800 seconds for the blendscomprising surfactants. Alcohol ethoxylate (activator 3) performedpoorly as a maximum torque of 30 cm-g was achieved at 1800 second forthe blend comprising it. Activator 12EO was the best performer among alltested surfactants.

In all cases, at the end of the test, the dilute latex solutions wereobserved to be fully dispersed, that is, no residual clumps oraggregates of material were observed.

TABLE 11 % Inversion and maximum torque for Polymer 4 blends with 2%activators Surfactant Inversion % Inversion % Max Torque Surfactant (%)(2 min) (5 min) (g · cm) 10EO 2.0 13.0 40.1 100 11EO 2.0 26.0 57.2 13012EO 2.0 47.8 73.0 120 13EO 2.0 25.3 56.9 130 Activator 1 2.0 36.6 61.8130 Activator 3 2.0 2.5 15.0 30 Activator 2 2.0 3.8 19.5 100 Activator 42.0 29.2 59.5 120

Example 6: Evaluation of Surfactants for Inversion of Non-Ionic InverseEmulsion Polymer in Tap Water

Latex: An un-activated polyacrylamide emulsion polymer (emulsion polymer5) without activating surfactant was used in this example.

Blend preparation and activator concentration: Polymer 5 blends with 2%activator were prepared by blending activator into the emulsion whilestirring at room temperature.

Conditions: The tap water from the City of Naperville, Ill. was used fortorque monitor experiments and was maintained at 22° C. An amount of theinvertible latex injected into the stirred water in the torque monitorapparatus yielded a dilute latex having 0.5% polymer.

Results: FIG. 10 depicts the inversion torque profiles at 25° C. forpolymer 5 (1% invert in SSW) blends with 2% activating surfactants.Table 12 shows induction period, hydration time and maximum torquevalues (in the plateau region) determined from torque experiments forpolymer 5 blends.

Discussion: The data of Table 12 and FIG. 10 demonstrate that, at 22°C., the blends of polymer 5 comprising 2 wt. % of a surfactantcomparable or faster inversion rates (as indicated by inversion % at 2min and 5 min) and comparable extent of inversion (as indicated bymaximum torque value) than polymer 5 blends comprising 2 wt. % of analcohol ethoxylate or a NPE ethoxylate surfactant in tap water. Amaximum torque in range of 230-230 cm-g was achieved within 700 secondsfor the blends comprising surfactants. Activator 12EO and activator 1were the best performers among all tested surfactants.

In all cases, at the end of the test, the dilute latex solutions wereobserved to be fully dispersed, that is, no residual clumps oraggregates of material were observed.

TABLE 12 % Inversion and maximum torque for Polymer 5 blends with 2%activators Induction Hydration Max Inversion Inversion period timeTorque Surfactant % @2 min % @5 min (sec) (sec) (g/cm) 10EO 48.3 79.6 30360 210 11EO 58.6 83.9 30 300 200 12EO 79.9 99.1 30 240 230 13EO 64.5100.0 50 540 230 Activator 1 90.0 100.0 30 180 250 Activator 2 43.9 75.645 300 200 Activator 3 73.3 82.0 50 740 220 Activator 4 38.4 78.3 45 540220 Activator 5 48.7 78.9 50 420 230

Example 7: Physical Properties of Novel Surfactants

In this example, the interfacial tension, cloud point and criticalmicelle concentration was determined for a series of ethoxylatesurfactants (1-((2-ethylhexyl)oxy)-3-phenoxypropan-2-ol ethoxylate)having 6 to 13 moles of EO groups.

1-((2-ethylhexyl)oxy)-3- nEO, where n Surfactants (Preparedphenoxypropan-2-ol indicates moles as in Examples 1A and ethoxylate ofEO units 1B)

The interfacial tension is a surface free energy of the interfacebetween two immiscible liquids (in this case, oil and water). Additionof surfactants reduces the interfacial tension. To achieve lowinterfacial tension, the surfactant partitions equally between twophases and the surfactant has a low affinity for both phases.

The interfacial tension between aqueous surfactant solution at 1% andcorn oil was measured using a spinning drop Tensiometer at 4000 rpm. Thetemperature was kept constant at 25° C. This value is actually dependenton temperature. The minimum interfacial value of different surfactantscan be different depending on the temperature and oil phase chosen.

The interphase tension for the ethoxylate surfactants measured usingcorn oil or dodecane as the light phase are described in Table 13.

TABLE 13 Interphase tension Interfacial tension Interfacial tension(mN/m) (25° C., (mN/m) (25° C., Surfactant light phase = corn oil, lightphase = dodecane, ID 4000 rpm) 4000 rpm) 6EO 0.49 0.13 7EO 0.35 0.10 8EO0.57 0.25 9EO 0.68 0.40 10EO 0.84 0.56 11EO 1.07 0.89 12EO 1.26 1.0313EO 1.63 1.65 NPE 9.5 0.837 0.40

The cloud point is the temperature at which the solution of a nonionicsurfactant turns cloudy. At this point, the solution has crossed a phaseboundary and the cloudy solution is an emulsion of a coacervate phase ina dilute phase.

The surfactant solution at 1 wt. % was heated slowly with stirring toensure consistent temperature throughout. The temperature at which thesolution started to turn cloudy was taken as a cloud point and depictedin Table 14 for the series of ethoxylate surfactants.

TABLE 14 Cloud points Surfactant ID Cloud Point (° C.) (+/−1 C.) 6EO <17EO 1.0 8EO 12.5 9EO 27.0 10EO 37.5 11EO 48.0 12EO 58.5 13EO 77.5 NP9.553.0

The critical micelle concentration (CMC) is a concentration at which amicelle starts to form in a solution having a surfactant. It can bemeasured through several physical property measurements. Here, it wasdetermined by measuring the surface tension of a surfactant solution atvarious concentrations. A semi log plot of concentration-surfacetemperature yielded a curve with a break or change in slope. At thebreak, the concentration was taken as the critical micelle concentration(CMC). Table 15 summarizes the critical micelle concentration for eachof the ethoxylate surfactants tested.

TABLE 15 Critical Micelle Concentrations Surfactant ID CMC (ppm) 6EO72.45 7EO 110.84 8EO 129.02 9EO 152.75 10EO 167.80 11EO 227.52 12EO350.73 13EO 451.00

Additional surfactants were prepared (example 2A and 2B) and testedgiving the following results. In this example, cloud point and criticalmicelle concentration was determined for a series of ethoxylatesurfactants(3,3′-((4-hydroxyphenyl)azanediyl)bis(1-((2-ethylhexyl)oxy)propan-2-ol)ethoxylate) having 10 to 24 moles of EO groups.

3,3′-((4- N-nEO, where n Surfactants hydroxyphenyl)azanediyl)bis(1-((2indicates moles of (Prepared as ethylhexyl)oxy)propan-2-ol) EO units (nis the in Examples ethoxylate sum of the o, p, 2A and 2B) and qintegers)

TABLE Surfactant Concentration (ppm) Cloud Point (° F.) CMC (ppm) N-10EO10,001 <36 — N-12EO 10,100 <36 — N-14EO 9,900 <36 — N-16EO 10,059 44 —N-18EO 9,898 68 — N-20EO 10,289 90 32 N-22EO 10,001 106 37 N-24EO 9,999124 42

Example 8: Non-APE Surfactants Demonstrate Good Soil Removal fromPremade Fabric Swatches

In this example, an alkaline detergent builder alone or in combinationwith the novel surfactants disclosed herein were subjected to a standardTergotometer test procedure to measure soil removal from premade fabricswatches (polyester or cotton). The test measured the ability of eachdetergent-surfactant combination to remove makeup from cotton, orlipstick from cotton or polyester. Table 16 describes the identity ofthe surfactants (1-((2-ethylhexyl)oxy)-3-phenoxypropan-2-ol ethoxylates)tested in this example.

TABLE 16 Surfactant moles of EO (“n”) Surfactant 1 7 Surfactant 2 8Surfactant 3 9 Surfactant 4 10 Surfactant 5 12

Premade polyester and cotton swatches purchased from Test Fabrics, Inc.were stamped with lipstick and/or make-up using a standardized methoddesigned to reduce variability in lipstick application to allow forrepeatable and consistent cleaning testing. Briefly, the stampingprocedure involved: coating the stamp in lipstick (Cover Girl #435 andTom Ford “Indian Rose” used) using an applicator and then dragging aclean edge, such as the edge of a stainless steel curtain across thestamp with the direction of the ridges. Ideally, the stamp was fullycoated in lipstick with ridges remaining visible. The fabric swatcheswere stamped, using the same quantity of pressure for each swatch. Thestamp was lifted lightly to allow the freshly stamped soil to beundisturbed.

Premade fluid make up on cotton swatches (code #C-S-17) were purchasedfrom the Center for Testmaterials B.V.

Soiled fabric swatches were then subjected to a standard Tergotometertest to measure effectiveness of detergent/surfactant combinations atremoving the soil. A tergotometer Model #7243ES, Serial MCC 14-813 fromTest Fabrics Inc was used along with 1 L pots and a water bath. Beforewashing, the initial values of the soiled swatches were read on theHunterLab COLOR QUEST Spectrophotometer to establish the initial “L”value. The tergotometer was set for 120° F. and one liter of 5 grainwater added to each of the six pots and allowed to equilabrate to 120°F.

The laundry solutions were weighed out and added to the tergotometerpots and agitated for 30 seconds to 1 minutes to mix and dissolve. Thecontroller was set for a 1 minute run time, with an RPM of 100 (standardRPM for most tests). Each swatch was added quickly in order to minimizedifferences in exposure time to the detergent systems. Each swatch wasagitated for 10 minute immediately after adding swatches and thenremoved and transferred to 1 L of cold 5 grain water to rinse. Theswatches were then removed from the cold water and further rinsed undercold 5 grain tap water. Excess moisture was removed by squeezing and theswatches were air dried on a Wypall paper towel. After drying, thespectrophotometer (HunterLab COLOR QUEST) was used to measure the final“L” value. The % soil removal was calculated from the difference betweenthe initial (before washing) L value and the final L value (afterwashing).

Table 17 describes the % soil removed from each of the followingcombinations: 1300 ppm Builder C (standard alkaline detergent builder),Builder C+NPE 9.5 (450 ppm), or 1300 ppm Builder C with Surfactants 1-5(450 ppm). NPE 9.5 is Nonylphenol with 9.5 moles of ethylene oxide.

TABLE 17 Makeup- Lipstick- Lipstick- Cotton Cotton Polyester DetergentCombination (% Removal) ST DEV (% Removal) ST DEV (% Removal) ST DEV1300 ppm Builder C 22.16 1.85 34.86 1.84 17.00 1.01 1300 ppm Builder C,44.20 2.80 53.29 1.23 64.91 0.59 450 ppm NPE 9.5 1300 ppm Builder C,37.70 2.84 47.77 0.32 45.09 0.70 450 ppm Surfactant 1 1300 ppm BuilderC, 36.12 2.30 50.51 2.25 63.34 0.55 450 ppm Surfactant 2 1300 ppmBuilder C, 42.61 1.86 52.01 0.94 66.43 0.30 450 ppm Surfactant 3 1300ppm Builder C, 42.18 1.65 53.11 1.93 63.78 0.86 450 ppm Surfactant 41300 ppm Builder C, 46.30 2.81 50.15 3.55 52.99 0.39 450 ppm Surfactant5

Example 9: Non-APE Surfactant Combinations Effective in RemovingLipstick from Homemade Swatches

The ability of the same detergent/surfactant compositions used inExample 8 to remove lipstick stains from homemade polyester swatches wastested in a similar way to Example 8. Major differences are describedbelow.

Lipstick (Tom Ford “Indian Rose”) was applied (stamped) onto eachhomemade polyester fabric swatches as described in Example 8. Washingwas done using the Tergetometer of Example 8 but the amount of pigmentremoved from each swatch (% removal) was determined using ImageJsoftware analyzing scanned images for the swatches before (A₁) and afterwashing (A2). Each image was processed to remove background (using awhite piece of paper as background) before quantification. A rectanglewas drawn on each image to contain the stamped lipstick (the same areasize was used in all measurements). The % area was then measured insidethis rectangle and used to determine the % pigment removal using thefollowing equation.

${{\%\mspace{14mu}{Removed}} = {\frac{A_{1} - A_{2}}{A_{1}} \times 100}},$where A₁ is the percent area before washing and A₂ is the percent areaafter washing.

Table 17 shows the results of soil removal from homemade swatches inthis experiment. Each detergent/surfactant combination performed equallyor superiorly to a control NPE surfactant.

TABLE 17 Chemistry % soil removal St Dev 1300 ppm Builder C 8.11 4.111300 ppm Builder C 85.78 4.61 450 ppm NPE 9.5 1300 ppm Builder C 61.481.45 450 ppm Surfactant 2 1300 ppm Builder C 92.89 1.14 450 ppmSurfactant 3 1300 ppm Builder C 89.87 1.86 450 ppm Surfactant 4

Example 10: Inventive Surfactants Effective at Butterfat Removal

A standard butterfat removal test method was used to screen surfactantsfor their ability to remove butter from a coupon (e.g., stainless steel,PS (Polysulfone), or PVDF (Polyvinylidene fluoride). Typical consumermaterials are made of PES (polyethersulfone) or PVDF material. Here, aPS coupon was used to represent the PES membrane surface.

A series of ethoxylated surfactants (6EO to 13EO and N-18EO to N-22EO)were tested alongside deionized (DI) water, Ethyl hexyl alcoholalkoxylate (Ecosurf EH-9), Nonylphenol with 9.5 moles of ethylene oxide(NPE 9.5). Each surfactant was used at a concentration of 200 or 600 ppmexcept EH-9 (always 1000 ppm).

Brand new, unused, coupons (1×3 in. PS coupons from Small Parts viaAmazon) were used for each surfactant tested. Each coupon was soaked inmethanol for 30 seconds and allowed to dry, then placed on a cookiesheet (lined with Wypall towels) in a 120° F. oven for 30 minutes. Aftercleaning and drying, each coupon was weighed on an analytical balance.Then a homogenous layer of room temperature butter (unsalted) wasapplied to the bottom 75% of each coupon using a 1″ wide foam brush.Overall, about 0.0250 to 0.0300 g of butter was applied to each coupon.Then the coupons were placed back on the cookie sheet and allowed to dryovernight before weighing a second time.

600 g of a test solution consisting of one surfactant (200 or 600 ppm,except for EH-9 (always 1000 ppm)) in DI water was prepared and added toa beaker along with a stir bar. The solution was heated to 120° F.(+/−2° F.), stir speed was set to 240 rpm, and NaOH added to bringsolution to pH 11. Note, each surfactant was tested in triplicate usingthree different coupons in three different beakers containing therelevant surfactant solution. Once prepared, the coupons were suspendedin the solution at a constant distance between the coupon and the centerof the beaker, with the soiled/butter side faced the center. The stirspeed was maintained at 240 rpm and the temperature maintained at 120°F. for 10 minutes. Then each coupon was removed and dipped three timesinto a separate beaker slowly overflowing with DI water (e.g., placedunder a running DI faucet). Each “dip” consisted of submerging thecoupon under the water for 2 seconds and removing for 2 seconds. Thecoupons were then placed on a paper towel to dry before returning to thecookie sheet where they dried overnight. The next day, they were weighedagain.

FIGS. 11A, 11B, and 11C show the percent soil removal calculated fromthe weight of the cleaned coupons compared to the dried soiled couponsfor 6EO to 13EO at 600 ppm (FIG. 11A), 6EO to 13EO at 200 ppm (FIG.11B), and N-18EO to N-22EO at 600 ppm (FIG. 11C). The ethoxylatedsurfactants (6EO to 13EO) performed well at removing butter residue ascompared to water or other standard surfactants (EH9 and NPE 9.5). Theethoxylated surfactants N-18EO to N-22EO performed progressively betterat higher moles of EO as compared to water or standard surfactant NPE9.5.

Example 11: Contact Angle Measurement of Surfactant Solutions

Polysulfone (PS) coupons (size 1″×2″) were prepared by removing theplastic film from each side, washed with soap and water and air dried. Aseries of surfactant solutions was prepared at the followingconcentrations in DI water: dodecyldimethylamine oxide (DDAO, 500 ppm),NPE 9.5 (500 ppm), 9EO (200 ppm and 600 ppm), and EH-9 (1000 ppm). Eachsolution was adjusted to a pH of 11 with NaOH.

The contact angle measurement for each solution was determined using anoptical Tensiometer (Attension Theta) with a temperature controlledchamber. This machine automates the temperature, recording time, andplacement of a droplet (4 μL) onto each coupon. The results for thecontact angle measurement for each solution over one minute (60 seconds)are plotted in FIG. 12. Both of the solutions containing the inventivesurfactant (9EO at 200 ppm or 600 ppm) performed similarly to controlsurfactants, NPE 9.5 or Ecosurf EH-9.

Example 12: Inventive Surfactants Effective at Red Soil Removal

A standard red soil removal test method was used to screen surfactantsfor their ability to remove red soil from a vinyl tile. Red soil mimicstypical consumer food soil.

A series of test solutions including either ethoxylated surfactants 9EOto N-24EO or nonylphenol with 9.5 moles of ethylene oxide (NPE 9.5) weretested. The test solutions were 72.1% zeolite softened water, 0.4%phosphoric acid 75% solution, 3.5% isopropyl alcohol, 6% tetrasodiumEDTA 40% solution, and either 18% ethoxylated surfactant or 18% NPE 9.5.Additional test solutions were Oasis Pro 16 at 8 oz/gallon (used as apositive control), and water (used as a negative control). Water forcontrols, solutions, etc. was 5 grain water (i.e. water with 5 grain pergallon) unless otherwise noted.

Vinyl tiles (cut to 3×3 in., manufactured by Flexco) were used for eachsolution tested. An average background measurement of the blank tileswas taken with a Hunter Mini Scan Colorimeter. Red soil was preparedimmediately before use and consisted of 39% lard, 39% corn oil, 20%whole egg powder, and 2% iron III oxide powder. The red soil wasprepared at 100° F. by combining the lard and the corn oil and mixing,adding the whole egg powder and mixing, and adding the iron III oxidepowder and mixing for 15 minutes. About 0.75 g of red soil was appliedto each tile with a foam brush. The soiled tiles were allowed to dryovernight. A colorimeter measurement of was taken of each tile.

Each tile was soaked for 60 seconds in 200 g of test solution. Soilremoval testing was conducted with a straight line abrasion machineapplying 2.0 lbs pressure through a cellulose sponge soaked with 80 g oftest solution. 4 back and forth motions of the sponge were followed by a90° rotation of the tile. This was repeated 4 times, for a total of 16back and forth motions. The tiles were gently rinsed with DI water andallowed to dry overnight in a dish rack. 5 measurements, approximatelyat the center and near each of the 4 corners, were taken per tile andaveraged for each tile.

FIG. 13 shows the percent soil removal calculated from the change incolorimeter readings before and after testing. Ethoxylated surfactantsperformed better compared to water.

Example 13: Foam Generation Behavior of Inventive Surfactants

A foam generation test was used to screen surfactants for their foamgeneration behavior. For various surfactant applications, high or lowfoam generation can be desirable.

A series of solutions including either ethoxylated surfactants (9EO orN-18EO) or nonylphenol with 9.5 moles of ethylene oxide (NPE 9.5) wastested. Each surfactant was used at a concentration of 1000 ppm.

Each test used 250 mL of solution which was equilibrated at the either20° C., 45° C., or 60° C. For each test, the solution was stirred for 10seconds at either 950 rpm or 1200 rpm, during which 99 measurements offoam volume were taken with a Sita R2000 Foam Analyzer.

FIG. 14A shows the height of foam created by 9EO in comparison to NPE9.5 at various temperatures and RPMs Foam generation by N-9EO was highin comparison to NPE 9.5 at 60° C. FIG. 14B shows the height of foamcreated by N-18EO in comparison to NPE 9.5 at various temperatures andspeeds. N-18EO demonstrated foam generation at 20° C. Foam generation byN-18EO was low in comparison to NPE 9.5. For N-18EO, there was littlefoam generation at 20° C. and almost none at 45° C. and 60° C.

Example 14: Foam Decay Behavior of Inventive Surfactants

A foam decay test was used to screen surfactants for their foam decaybehavior. For various surfactant applications, fast or slow foam decaycan be desirable.

A series of solutions including either ethoxylated surfactants (9EO orN-18EO) or nonylphenol with 9.5 moles of ethylene oxide (NPE 9.5) wastested. Each surfactant was used at a concentration of 1000 ppm.

Each test used 250 mL of solution which was equilibrated at the either20° C., 45° C., or 60° C. For each test, the solution was stirred for 10seconds at either 950 rpm or 1200 rpm to generate foam. Measurements offoam volume were taken with a Sita R2000 Foam Analyzer every 10 secondsfor upwards of 15 minutes, or until the foam volume reached 0 mL.

FIG. 15A shows the height of foam created by 9EO in comparison to NPE9.5 at various temperatures and speeds. FIG. 15B shows the height offoam created by N-18EO in comparison to NPE 9.5 at various temperaturesand speeds. Foam decay of N-18EO and 9EO solutions was fast and similarto that of NPE 9.5.

When introducing elements of the present invention or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

In view of the above, it will be seen that the several objects of theinvention are achieved and other advantageous results attained.

As various changes could be made in the above compositions and processeswithout departing from the scope of the invention, it is intended thatall matter contained in the above description and shown in theaccompanying drawings shall be interpreted as illustrative and not in alimiting sense.

The invention claimed is:
 1. A compound having has the structure ofFormula 3:

wherein R₁, R₂, R₄, and R₅ are independently hydrogen, alkyl, alkoxyl,or Z; and Z₁, Z₂, and Z independently have a structure of moiety A ormoiety B:

wherein X is —O— or —N(R₁₀)—; n is an integer from 0 to 5; R₆ and R₉ areindependently hydrogen or alkyl; R₇ is alkyl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₀ is hydrogen, alkyl, or Z;R₁₁ is hydrogen or alkyl; m is an integer from 3 to 20; z is an integerfrom 1 to
 10. 2. The compound of claim 1, wherein R₁, R₂, R₄, and R₅ areindependently hydrogen or C₁ to C₄ alkyl.
 3. The compound of claim 2,wherein R₁, R₂, R₄, and R₅ are hydrogen.
 4. The compound of claim 2,wherein R₆ and R₉ are hydrogen.
 5. The compound of claim 1, wherein R₈is hydrogen or methyl.
 6. The compound of claim 1, wherein R₇ is—(CH₂)z-O—R₁₁ and z is 1 to
 3. 7. The compound of claim 6, wherein R₁₁is C₄ to C₂₂ alkyl.
 8. The compound of claim 7, wherein X is —O— or—N(R₁₀)—.
 9. The compound of claim 8, wherein X is —O—.
 10. The compoundof claim 8, wherein X is —N(R₁₀)— and R₁₀ is hydrogen.
 11. The compoundof claim 1, wherein Z has the structure of moiety A, X is —O—, n is 0,R₁, R₂, R₄, R₅ are hydrogen, R₆ and R₉ are hydrogen, R₇ is (CH₂)z-O—R₁₁,z is 1, R₈ is hydrogen, R₁₁ is 2-ethylhexyl, and m is an integer from 7to
 13. 12. A compound of Formula 4 having the following structure:

wherein R₁, R₂, R₄, and R₅ are independently hydrogen, alkyl, oralkoxyl; Z₁ is has a structure of moiety C

Z₂ has a structure of moiety D

n is an integer from 0 to 5; R₇ is alkyl, or —(CH₂)z-O—R₁₁, R₈ isindependently hydrogen, alkyl, or aryl; R₁₁ is hydrogen or alkyl; m isan integer from 3 to 30; and z is an integer from 0 to
 6. 13. Thecompound of claim 12, wherein n is 0, R₇ is —(CH₂)z-O—R₁₁, R₈ ishydrogen, Rug is 2-ethylhexyl, m is an integer from 10 to 30, and zis
 1. 14. A polymer composition comprising: a water-in-oil emulsioncomprising an aqueous phase comprising water and a water-soluble orwater-dispersible polymer, and an oil phase comprising an oil and anemulsifying agent; and an inversion surfactant comprising the compoundof claim
 1. 15. A detergent composition comprising a building agent anda surfactant, the surfactant comprising the compound of claim
 1. 16. Amethod of cleaning a membrane, the method comprising contacting themembrane with a cleaning composition, the cleaning compositioncomprising the compound of claim 1.